Inhibition of Pitting On Carbon Steel

INHIBITION OF PITTING ON CARBON STEEL
Ismarullizam Mohd Ismail
Submitted in accordance with the requirements for the degree of
Doctor of Philosophy
The University of Leeds

Faculty of Mechanical Engineering
October, 2011
The candidate confirms that the work submitted is his own and that appropriate credit
has been given where reference as been made to the work of others.
This copy has been supplied on the understanding that it is copyright material and that
no quotation from the thesis may be published without proper acknowledgement.
11
Acknowledgements
First and foremost, I would like to acknowledge God Almighty for blessing
me with health, strength and motivation to persevere through this journey.
I am extremely grateful to my supervIsor, Professor Anne Neville for her

constant guidance and encouragement and for her unique way of teaching that always
served to motivate and extrapolate my skill and knowledge, making me enthusiastic
towards my research and making me a better researcher. I also express my special
thanks to my co-supervisor Dr. Xinming Hu for his guidance, encouragement and
ability to lend a hand whenever I need his support.
I would like to express my gratitude to University of Leeds, England and

Baker Hughes for their project funding, especially to Wai Mok, Jeremy Moloney,
Chris Gamble, Vladimir Jovancicevic and Sunder Ramachandran for the discussion,
guidance and support during this studies. I would also like to acknowledge MARA
(Malaysian Government Student Department) for their support during my studies.
I am grateful to the present and past members of iETSI Research Group

especially Rick, Michael, Azzura, Khalid, Kuldeep, Abinesh, John, Penny, Juan,
Akbar, Benissa, Violette, Wendy, Eleftheria, Nasser, Nassim, Laura, Shariar, Jane,
Hui, Louise, James, Ike, Thibaut, Feth-Allah and Faisal Reza for the discussion and
friendships. I also would like thanks the iETSI staff Graham Jakeman, Ron Cellier,
John Groves, Jackie Kidd, Fiona Slade, Andy Barnett, Dr. Nik Kapur, Dr. Chun
Wang, Dr. Thomas Liskiewicz and Dr. Ardian Morina for their guidance and support.
Special thanks Adrian Eagles, John Harrington and Richard Walshaw for their support
and guidance in using the surface analysis equipment.
I would like to express my appreciation and dedicate this work to my beloved

wife, Jullyza Teoh and my daughters Aisyah and Balqis for their love, motivation,
constant patience, encouragement and always on my side during this studies. Special
thanks to my family back home; my parents Mohd Ismail and Norakin and my in-laws
Hassan Teoh and Junaidah and my brothers and sisters for their love and support.
"L;-r.·
IJe IS a J Durney .... .. . "
111
Abstract
Carbon dioxide and hydrogen sulphide pitting related failures are a pnme
concern in oil and gas internal pipelines. Often, these types of failure have a great
impact on safety and environmental matters and can cause severe financial
consequences to the operator.
Chemical inhibitors have been used to provide effective protection for the
asset whether it is due to localised corrosion or general corrosion. More often than
not, the operating conditions determine the type of corrosion product film produced
on the carbon steel and in tum influence the type of corrosion inhibitor to provide
effective protection for the asset.
In order to develop supenor localised corrosIOn inhibitors, a better

understanding of the mechanisms of the action and interaction of pitting and the
corrosion products are required. An extensive study on the corrosion film, pitting
growth and inhibition of pitting corrosion of carbon steel X65 in sweet and sour
conditions has been carried out using electrochemical methods and various post test
surface analysis techniques. The results revealed that both phosphate ester and
imidazoline inhibitors showed excellent performance to stop pit propagation in sweet
conditions if the optimum concentration is applied.
An in-situ monitoring technique for assessing real and artificial pit growth on
X65 carbon steel surfaces in sweet and sour conditions has been developed to
investigate the inhibitor action on the pits and surrounding corrosion films.
Assessments of the surface chemistry around the pits by ¥fIR analysis revealed that
there are two different mechanisms focused on inhibiting pitting corrosion. The first
mechanism revealed that the inhibitor adsorbs at the pit site and is absent on the
surrounding film and the second mechanism revealed that the inhibitor adsorbs both
on the pit site and on the surrounding films.
IV
Table of Contents
Acknowledgements ...................................................................................................... .ii

Abstract .........................................................................................................................iii
Table of contents ......................................................................................................... jv
List of figures ................................................................................................................xi
List of tables .............................................................................................................xxiv
Abbreviations..............................................................................................................xxv
1.0 Introduction....................................................................................................... 1
1.1 Overview of oilfield corrosion as a global challenge ......................... 1
1.2 Carbon steel X65 pipeline operation in the oilfield industry ............ 1
1.3 Carbon steel pitting in sweet environments ........................................ 3
1.4 Carbon steel pitting in sour environments .......................................... 4
1.5 Inhibition of corrosion in the oilfield industry..................................... 5
1.6 Objectives of the research ..................................................................... 6
1.7 Scope of work ....................................................................................... 7
1.8 Outline of the thesis ............................................................................... 7
2.0 Fundamental theory ........................................................................................9

2.1 Corrosion ...............................................................................................9
2.2 Electrochemical reactions of aqueous corrosion ................................. 9
2.3 Thermodynamics of corrosion reaction ............................................... 10
2.4 Free energy............................................................................................. 10

2.5 Kinetics of corrosion reactions ............................................................. 1 1
2.6 Polarisation ............................................................................................ 11
2.7 Mixed potential electrodes.................................................................... 12
2.8 DC linear polarisation test method....................................................... 13
2.9 Type of corrosion................................................................................... 15
2.9.1 General corrosion ...................................................................... 15
2.9.2 Galvanic corrosion..................................................................... 15
2.9.3 Crevice corrosion....................................................................... 16
2.9"+ Intergranular corrosion.............................................................. 16
2.10 Pitting corrosion..................................................................................... 16
v
2.10.1 Mechanisms of pitting corrosion ............................................ .17

2.10.2 Pitting shape and growth......................................................... .18
2.10.3 Evaluation of pitting damage ................................................. .18
2.11 Corrosion inhibitors............................................................................... 18
3.0 Literature review..................................................................................................20

3.1 Sweet corrosion in carbon steel ............................................................ 20
3.1.1 Electrochemistry of sweet corrosion ..................................... .20
3.1.2 Effect of supersaturation.......................................................... .21
3.1.3 Effect of temperature................................................................ .22
3.1.4 Influence of pH..........................................................................23
3.1.5 Influence of carbon dioxide pressure ...................................... .2-+
3.2 Sweet corrosion films ............................................................................ 24
3.2.1 Transparent films ....................................................................... 25
3.2.2 Iron carbonate film ....................................................................25
3.2.3 Iron carbide film ........................................................................26
3.2.4 Iron carbonate plus iron carbide film .......................................26
3.3 Sweet pitting corrosion on carbon steel ............................................... 28
3.3.1 Pitting corrosion failure ........................................................... .28
3.3.2 Pit initiation in sweet conditions ..............................................29
3.3.3 Metastable pits........................................................................... 29
3.3.4 Stable pits...................................................................................30
3.3.5 Pits propagation in sweet environments.................................. .31
3.4 Sweet corrosion inhibitors .................................................................... 32
3.4.1 Imidazoline inhibitor................................................................ .33
3.4.2 Phosphate ester inhibitor.......................................................... .33
3.5 Sour corrosion in carbon steel .............................................................. 34
3.5.1 Electrochemistry of sour corrosion ......................................... .35
3.5.2 Influence of operating condition.............................................. .36
3.5.2.1 H2S concentration......................................................................36
3.5.2.2 Temperature...............................................................................36
3.5.2.3 Solution composition................................................................ .37
3.6 Sour corrosion films .............................................................................. 38
3.6.1 Mackinawite...............................................................................-+ 1
vi
3.6.2 Pyrite ..........................................................................................-1-2

3.6.3 Pyrrhotite....................................................................................-1-2
3.6.4 Amorphous FeS and cubic FeS ................................................43
3.6.5 Smythite and greigite.................................................................-1-3
3.7 Sour pitting corrosion on carbon steel.................................................. 43
3.7.1 Sour pitting corrosion process ..................................................45
3.7.2 Sour pitting corrosion initiation................................................45
3. 7 .3 Sour pitting corrosion propagation...........................................46
3.8 Sour corrosion inhibitor ........................................................................ 47
3.8.1 Types of sour corrosion inhibition ...........................................49
3.9 Environmentally friendly corrosion inhibitors .................................... 50
3.9.1 Corrosion inhibitor legislation.................................................51
3.10 Artificial pitting experiment ................................................................. 52
3.11 In-situ pitting experiment...................................................................... 54
3.12 Surface analysis .................................................................................... 55
3.13 Literature review summary................................................................... 57
4.0 In-situ visualisation rig and sour rig design and setup...............................59
4.1 Sweet in-situ pitting riK ........................................................................ 59
4.2 Sour experiment rig ............................................................................... 61
4.2.1 Hydrogen sulphide safety..........................................................63
4.2.2 Sour experiment system............................................................63
4.2.3 Operation and emergency procedure of the rigs......................64
4.2.4 Experiment setup procedure .....................................................65
4.2.5 Completion of the experiment procedure.................................65
4.2.6 Helium pressure test procedure ................................................66
4.2.7 Cleaning the scrubber procedure ..............................................66
5.0 Experimental section........................................................................................67

5.1 Material used for study. ......................................................................... 67
5.2 Sample preparation procedure .............................................................. 67
5.3 Corrosion testing setup.......................................................................... 68
5.4 Ill-situ camera setup. .............................................................................. 68
5.5 Experiment procedure for surface film investigation for sweet
Vll
and sour conditions ...............................................................................68

5.6 Experiment procedure for natural pitting test for sweet and sour
conditions ...............................................................................................71
5.7 Experimental procedure for artificial pitting test for sweet and
sour conditions .......................................................................................73
5.8 Post test analysis.................................................................................... 75
5.8.1 Talysurf 5 profilometry............................................................ .75
5.8.2 White light interferometer ....................................................... .75
5.8.3 Optical microscopy .................................................................. .76
5.8.4 Secondary Electron Microscopy and Energy Dispersive
X-ray Analysis (SEM-EDX) ................................................... 76
5.8.5 Atomic Force Microscopy (AFM) .......................................... .76
5.8.6 Focused Ion Beam (FIBt ........................................................ .76
5.8.7 X-ray Photoelectron Spectroscopy (XPSt ............................. .77
5.8.8 Fourier Transform InfraRed (FTIRL ..................................... .78
5.9 Inhibitors ................................................................................................ 78
5.9.1 Phosphate ester inhibitor.......................................................... .79
5.9.2 Imidazoline inhibitor................................................................ .79
5.9.3 Nonoxoynol-6 phosphate inhibitor.......................................... .79
5.9.4 Poly alkyl pyridines inhibitor ...................................................80
6.0 Results - Characterisation of the surface film formed from sweet

and sour corrosion ........................................................................................... 82
6.1 Corrosion current measurement............................................................ 82
6.1.1 Sweet experiments.....................................................................82
6.1.2 Sour experiments .......................................................................84
6.2 SEM analysis ......................................................................................... 85
6.2.1 Sweet experiments.....................................................................85
6.2.2 Sour experiments .......................................................................91
6.3 FIB/SEM analysis.................................................................................. 93
6.-+ AFM analysis......................................................................................... 95
6.5 EDX analysis ......................................................................................... 97
6.6 XPS analysis .......................................................................................... 100
6.6.1 Evolution of C 1s peaks .......................................................... .1 00
VllI
6.6.2 Evolution of Fe 2p3/2 peaks .................................................... ) 03

6.7 Summary ............................................................................................... 108
7.0 Results - Investigation of pitting corrosion in sweet and sour

conditions............................................................................................................ 109
7.1 Pitting growth ....................................................................................... l09
7.1.1 Corrosion current measurement for sweet experiments......... ) 09
7.1.2 Corrosion current measurement for sour experiments ........... .1 14-
7.1.3 Pit depth analysis for sweet experiments ................................ ) 15
7.1.4 Pit depth analysis of sour experiments.................................... ) 18
7.2 Inhibition of pitting in sweet experiment............................................. 120
7.2.1 Corrosion current measurement for phosphate ester
inhibitor...................................................................................... 120
7.2.2 Corrosion current measurement for imidazoline inhibitors... ) 22
7.2.3 Pit depth analysis for phosphate ester inhibitor....................... 124-
7.2.4 Pit depth analysis for imidazoline inhibitors ........................... 126
7.3 Summary ............................................................................................... 128
8.0 Results - Evaluation of inhibitor performance using artificial pit

technique under sweet conditions ................................................................. 129
8.1 Corrosion current measurement............................................................ 129
8.1.1 Effect of phosphate ester............................................................. 131
8.1.2 Effect ofimidazoline ................................................................... 133
8.2 In-situ camera monitoring techniques.................................................. 134
8.2.1 Effect of phosphate ester............................................................ ) 36
8.2.2 Effect ofimidazoline ................................................................... l37
8.3 Pit depth analysis ................................................................................... 137
8.3.2 Effect of imidazoline ................................................................. ..142
8,4 Fourier Transform InfraRed (FTIR) spectroscopy.............................. 1+4
8,4.2 Effect of imidazoline ................................................................... 148
8.5 Summary ............................................................................................... 150
IX
9.0 Results - Evaluation of inhibitor performance using artificial pit

technique under sour conditions.................................................................... 151
9.1 Corrosion current measurement................................................................. 151
9.1.1 Effect of nonoxynol-6 phosphate .............................................. ) 53
9.1.2 Effect of poly alkyl pyridines .................................................... )53
9.2 In-situ camera monitoring techniques.................................................. 157
9.2.1 Effect of nonoxynol-6 phosphate .............................................. .158
9.2.2 Effect of poly alkyl pyridine ...................................................... ) 58
9.3 Pit depth analysis ................................................................................... 159
9.3.1 Effect of nonoxynol-6 phosphate .............................................. ) 61
9.3.2 Effect of poly alkyl pyridines .................................................... )63
904 Fourier Transform InfraRed spectroscopy (FTIRt ............................ 165
904.1 Effect of nonoxynol-6 phosphate ............................................... 166
904.2 Effect of poly alkyl pyridines ..................................................... 169
9.5 Summary ............................................................................................... 172
10.0 Discussion..........................................................................................................173
10.1 Sweet film behaviour ............................................................................ 173
10.2 Sour film behaviour............................................................................... 17 7
10.3 Sweet film breakdown and pit initiation.............................................. 182
1004 Sour pitting behaviour........................................................................... 186
10.5 Inhibition of pitting propagation by phosphate esters in sweet
environment 188
10.6 Inhibition of pitting propagation by imidazoline in sweet
environment............................................................................................ 191
10.7 In-situ monitoring of artificial pit growth under sweet condition ...... 19-+
10.8 The effect of phosphate ester on artificial pit growth under sweet
condition ................................................................................................. 198

10.9 The effect of imidazoline on artificial pit growth under sweet
condition.................................................................................................200
10.10 In-situ monitoring of artificial pit growth under sour condition ........ 202
10.11 The effect of nonoxynol-6 phosphate on artificial pit growth
under s\\'eet conditions ......................................................................... ,20-+
10.12 The effect of poly alkyl pridines on artificial pit growth under
x
sweet conditions ......................................................................................206
11.0 Conclusion and future work ...........................................................................209

11.1 Conclusions............................................................................................ 209
11.1.1 In-situ visualisation rig and sour rig design and setup............ 209
11.1.2 Characterisation of the surface film formed from sweet
and sour corrosion..................................................................... 210

11.1.3 Investigation of pitting corrosion in sweet and sour
conditions .................................................................................. 211

11.1.4 Evaluation of inhibitor performance using the artificial pit
technique under sweet conditions ............................................ 212
11.1.5 Evaluation of inhibitor performance using the artificial pit
technique under sour conditions............................................... 213
11.2 Industrial relevance................................................................................ 21-+
11.3 Recommendations for future research.................................................. 215
References ......................................................................................................................216
Appendix ........................................................................................................................232
Appendix A Operational and emergency procedure of the sour rig, ....................... .232
Appendix B Helium pressure test procedure for sour rig .........................................233
Appendix C Cleaning the scrubber procedure for sour rig ...................................... 23-+
Xl
List of Figures
Figure 1-1: X65 carbon steel pipeline transporting production fluid from
offshore to onshore facilities .................................................................2
Figure 1-2: Localised corrosion in pipeline ............................................................ .3
Figure 1-3: Leaking in subsea pipeline due to internal corrosion ......................... .3
Figure 2-1: Combined polarisation curve-activation and concentration
polarisation ............................................................................................. 11
Figure 2-2: Corrosion characteristics of active-passive metal as a function
of the solution oxidising power (electrode potential) .......................... 12
Figure 2-3: Schematic representation of electrode kinetic behaviour of pure
iron in acid solution ............................................................................... 13
Figure 2-4: Three electrode test cell schematic 13
Figure 2-5: Applied-current linear polarisation curve............................................. 15
Figure 2-6: Mechanisms of film breakdown............................................................. 17
Figure 3-1: Predicted effect of Fe 2+ concentration on the corrosion rate
for T = 80°C, pH 6.6, PC02 = 0.54 bar and V = 1rn1s .......................... .22
Figure 3-2 : Predicted effect of temperature on the corrosion rate for
pH 6.6, PC02 = 0.54 bar, C Fe2 + = 250ppm, and V = 1rn1s.....................23
Figure 3-3: Predicted effect of pH on the corrosion rate for T = 80°C,
PC02 = 0.54 bar, CFe 2+ = 250ppm, and V = 1rn1s ..................................24
Figure 3-4: Morphologies observed for protective and unprotective
corrosion layers ......................................................................................27
Figure 3-5: SEM image of a cross section of a steel specimen including
iron carbonate scale. Exposed for 10 hat T = 80°C, pH = 5.6,
PC02 = 0.54 bar, CFe 2+ = 250ppm, and V = 1rn1s ................................. .27
Figure 3-6: Variations in the cross-sectional shape of pits .....................................30
Figure 3-7: Calculated pH effect on solubility of FeC03 and the grey
zone at T = 80°C, PC02 = 0.53bar, 10/c NaCI........................................ .3 1
Figure 3-8: Generalised structure of saturated straight chain imidazolines.......... .3 3
Figure 3-9: Generalised structure of phosphate esters ........................................... )-l
Figure 3-10: Temperature-composition diagram for the iron sulphide system ...... .3 8
Figure 3-11: SEM image of FeS after 3 hours exposed time at 50C:e H 2S,
50lle C02, 60°C, pH 5 ............................................................................39
Xll
Figure 3-12: SEM image of FeS after 24 hours exposed time at 509c H 2S.
509c CO 2 • 60°C, pH 5 ............................................................................39

Figure 3-13: Corrosion regimes in C0 2/H 2S corrosion.............................................-l-0
Figure 3-14: Corrosion product relationship..............................................................41
Figure 3-15: Summary of the major iron sulphur inter relationships in
aqueous solution.....................................................................................-l-.2
Figure 3-16: SEM cross-section image showing pit growth under film on
X65 carbon steel. Exposed for 30 days at T = 60°C,
pH = 6, Pe02 = 0.77Mpa, H 2S at 25ppm, and V = 1rn1s .....................-l--+
Figure 3-17: Pit depth measurements and pit counts for blank tests and
inhibitors.................................................................................................44
Figure 3-18: SEM picture of a pit filled with corrosion product..............................46
Figure 3-19: SEM image after 14 Days at 3% NaCI, pH 6, 689Kpa H 2S................47
Figure 3-20: SEM image after 14 Days at 3% NaCI, pH 6, 689Kpa H 2S with
inhibitor...................................................................................................48
Figure 3-21: Molecular structure of a) pyridine, b) pyrrole and c) imidazole.........50
Figure 3-22: Schematic of two-compartment cell for pencil artificial pit

experiment..............................................................................................53
Figure 3-23: Typical surface topography of FeC0 3 film at the end of
dissolution process at 10000rpm velocity, pH 5.8 ...............................5-l-
Figure 3-24: XPS survey spectra recorded from steel coupons exposed for 96
hours to deaerated aqueous solution of 59c NaCI CH 3COOH
saturated with H2S a) no inhibitor, b) with inhibitor added ................56
Figure 4-1: Specimens for in-situ rig, .......................................................................59
Figure 4-2: In-situ sweet pitting rig setup................................................................60
Figure 4-3: In-situ pitting rig system........................................................................61
Figure 4-4: Artificial pitting image using different magnifications .......................61
Figure 4-5: In-situ sour rig test setup .......................................................................62
Figure 4-6: In-situ sour rig testing system ...............................................................63
Figure -+-7: Sour experiment system diagram..........................................................64
Figure 5-1: Experimental setup for sweet tests........................................................69
Figure 5-2: Artificial pit depth of X65 carbon steel before the test ...................... .7 3
Figure 5-3: XPS survey scan for X65 carbon steel surface before the test............78
Xlll
Figure 5-4: Nominal structure of phosphate ester inhibitor...................................}9

Figure 5-5 Nominal structure of imidazoline inhibitor..........................................79
Figure 5-6: Nominal structure of nonoxoynol-6 phosphate inhibitor ....................80
Figure 5-7: Nominal structure of poly alkyl pyridines inhibitor ............................ 80
Figure 5-8: Nominal structure of pyridine components quatemise the
benzyl chloride ....................................................................................... 81
Figure 6-1: Corrosion rate versus time for short tests on X65 carbon in
CO 2-saturated lO/C NaCl brine at 50°C and 1 bar total pressure..........83
Figure 6-2: Corrosion rate versus time for long tests on X65 carbon in
CO 2-saturated lO/C NaCl brine at 50°C and 1 bar total pressure..........83
Figure 6-3: Corrosion rate versus time at 3.3 bar H2S and 5.0 bar CO 2 at
various temperatures ..............................................................................84

Figure 6-4: SEM image of the specimens before the experiments.........................86
Figure 6-5: SEM image of the sweet pre-corrosion specimens at 50°C
after 0.5 hours.........................................................................................86

Figure 6-6: SEM image of the sweet pre-corrosion specimens at 50°C after
1 hour ......................................................................................................87
2.5 hours .................................................................................................87
4 hours ....................................................................................................88
8 hours ....................................................................................................88
24 hours ..................................................................................................89
72 hours ..................................................................................................89
Figure 6-12: SEM image of the cross-section of sweet pre-corrosion at 50°C
after 0.5 hours.........................................................................................90
after 2.5 hours.........................................................................................90
after 24 hours..........................................................................................91
Figure 6-15: SE~l image of the sour corrosion specimens at 90°C for 70 hours ....9 2
XIV
Figure 6-16: SEM image of the sour corrosion specimens at 15°C after
70 hours ..................................................................................................9'-
Figure 6-17: SEM image of the sour corrosion specimens at 15°C for 1st
hour and increased to 90°C after 70 hours............................................93
Figure 6-18: Fm/SEM image of the cross-section for sweet pre-corrosion
at 50°C after 0.5 hours ...........................................................................94
Figure 6-19: Fm-SEM image of undissolved Fe3C after 0.5 hours for X65
carbon steel in CO2 saturated 100c NaCI brine at 50°C and 1 bar
total pressure............................................................................................95
Figure 6-20: AFM image of the sweet pre-corrosion surface after
difference exposure times at 50°C. a) 0 hour; b) 0.5 hours;
c) 1 hour; d) 2.5 hours; e) 4 hours.........................................................96
Figure 6- 21: Film thickness versus corrosion rate versus time for X65 carbon
in CO 2 saturated IO/C NaCI brine at 50°C and 1 bar total pressure......97
Figure 6-22: Film thickness and Feo/c content versus time for X65 carbon steel
in CO 2 saturated 100c NaCI brine at 50°C and 1 bar total pressure......98
Figure 6-23: Film thickness versus Fe% content for X65 carbon steel in
C02 saturated 1% NaCI brine at 50°C and 1 bar total pressure .........98
Figure 6-24: SEM image after 24 hours for X65 carbon steel in CO 2
saturated 100c NaCl brine at 50°C and 1 bar total pressure .................99
Figure 6-25: Surface scan of C Is spectrum and curve fitting for 0 hour
(as-polished sample) .............................................................................. 101
Figure 6-26: Surface scan of CIs spectrum and curve fitting for 2.5 hour
sweet pre-corrosion at 50°C .................................................................. l0 I
Figure 6-27: Surface scan of CIs spectrum and curve fitting for the sour
corrosion after 70 hours at 90°C............................................................ 102
Figure 6-28: Sputtering of Fe 2P312 spectrum for O-hour
(as polished surface) specimen at Os and after 60s etching................ )04
Figure 6-29: Surface scan of Fe 2P3/2 spectrum and curve fitting for O-hour
(as-polished sample) after 60s etching ............................................... ..1 04
Figure 6-30: Surface scan of Fe 2PV2 spectrum and curve fitting for 2.S-hour
sweet pre-corrosion at 50°C after 60s etching.................................... ) 06
Figure 6-31: Surface scan of Fe 2P3/2 spectrum and curve fitting for the
sour corrosion after 70 hours at 90°C after 60s etching...................... ) 06
xv
Figure 6-32: Surface scan of Fe 2pv! spectrum and curve fitting for the
sour corrosion after 70 hours at 15°C after 60s etching ...................... l07
Figure 6-33: Summary of XPS results; a) Uncorroded b) Sweet at 50°C
after 2.5 hours, c) Sour at 90°C after 70 hours, d) Sour at 15°C
after 70 hours.......................................................................................... 107

Figure 7-1: Corrosion rate versus time for the X65 carbon steel in CO2
saturated, 10% NaCI brine at 80°C, pH 5.65 and 1000ppm Fe 2+....... .110
Figure 7-2: SEM cross-section image of X65 carbon steel in CO2
saturated 10% NaCl, pH 5.65 at 80°C after -+ hours ........................... .110
Figure 7-3: In-situ camera observation on pit initiation on X65 carbon steel in
CO 2 saturated 10ge NaCI, pH 5.65, 1000ppm Fe 2+ at 80°C
from 5 hours to 8 hours ......................................................................... .11 1

Figure 7-4: In-situ camera observation on pit propagation on X65 carbon
steel in CO 2 saturated 10ge NaCI, pH 5.65, 1000ppm Fe 2+ at 80°C
from 10 hours to 150 hours .................................................................. ) 12

Figure 7-5: SEM surface image on X65 carbon steel in CO 2 saturated
10ge NaCL pH 5.65, 1000ppm Fe-"+ at 80°C after 15 0 hours 113
Figure 7-6: SEM cross-section on X65 carbon steel in CO 2 saturated
2
10ge NaCI, pH 5.65, 1000ppm Fe + at 80°C after 150 hours ............. .113
Figure 7-7: Corrosion rate versus time for the X65 carbon steel in
10ge H 2S, 90ge C02 saturated, 10ge NaCI brine at 80°C.................... ) 1-+
Figure 7-8: Corrosion rate versus time for the X65 carbon steel in
10% H2S, 90%C02 saturated, 10% NaCI brine at 80°C, pH 5.65 ..... .115
Figure 7-9: SEM image on X65 carbon steel in 10ge H2S, 90% CO:! in
10ge NaCI at 80°C in sour after 96 hours ............................................ .115
Figure 7-10: Profilometry analysis for 150 hour specimens of X65 carbon
in CO 2 saturated 10ge NaCI brine at 80°C, pH 5.65, 1000ppm Fe 2+
and 1 bar CO 2 : a) 2D view of pits surface, b) Cross-section
for x-profile from 2D view, c) 3D view of pits surface,
d) Cross-section for Y profile for Y profile from 2D view,
e) 3D view of pits surface, f) Cross-section from 3D view pits......... .116
Figure 7-11: Maximum pit depth and average of 3 maximum pit depth
of X65 carbon in CO 2 saturated 10 e e NaCl brine at 80°e,
pH 5.65. 1000ppm Fe 2+ and 1 bar total pressure at different times ... ) 17
XVI
Figure 7 -12: Pit depth of X65 carbon in 10% H2S, 90% CO 2 saturated,
109c NaCI brine at 80°C ........................................................................ 118
Figure 7-13: Profilometer analysis ofX65 carbon steel in 10% H2S,
90% CO2 saturated, 10% NaCI brine at 80°C, pH 5.65; a) 2D yie\\
of pits surface after 4 hours, b) Cross-section from 2D view pits after

4 hours. c) 2D view of pits surface after 96 hours, d) Cross-section
for X profile from 2D view, e) 3D view of pits surface after 96
hours, f) Cross-section for y-profile from 2D view ............................ .119
Figure 7-14: Corrosion rate versus time for the X65 carbon steel in CO 2
saturated, 10% NaCI brine at 80°C, pH 5.65 and 1000ppm Fe 2+
with different concentrations of phosphate ester ................................ .120
Figure 7-15: Expanded version of corrosion rate versus time for the X65
carbon steel in CO2 saturated, 10% NaCI brine at 80°C, pH 5.65
and 1000ppm Fe 2+ with different concentrations of phosphate
ester ........................................................................................................ 121

Figure 7-16: Corrosion rate versus time for the X65 carbon steel in CO 2
saturated, 10% NaCl brine at 80°C, pH 5.65 and 1000ppm Fe 2+
with different concentrations of imidazoline....................................... .123
Figure 7-17: Expanded version of corrosion rate versus time for the X65
carbon steel in CO 2 saturated, 100/c NaCI brine at 80°C, pH 5.65
2
and 1000ppm Fe + with different concentrations of imidazoline ...... .123
Figure 7-18: Maximum pit depth and average of 3 maximum pit depth of
X65 carbon in CO2 saturated 10% NaCI brine at 80°C,
pH5.65, 1000ppm Fe 2+ with different concentrations of phosphate
ester......................................................................................................... 124
Figure 7-19: Profilometer analysis of X65 carbon steel in CO2 saturated
10% NaCI brine at 80°C, pH 5.65, 1000ppm Fe 2+ with
different concentrations of phosphate ester; a) 2D view of pits
surface at 100ppm, b) Cross-section from 2D view pits at 100ppm,
c) 3D view of pits surface at 100ppm, d) Cross-section for X
profile from 2D view at 100ppm, e) 2D view of pits surface at
10ppm, f) Cross-section for y-profile from 2D view at lOppm ......... .125
Figure 7-20: Maximum pit depth and average of 3 maximum pit depth of
X65 carbon in CO 2 saturated 100/e NaCI brine at 80°e,
XVll
2
pH5.65, 1000ppm Fe + with different concentrations of
imidazoline .............................................................................................126
Figure 7-21: Profilometer analysis of X65 carbon steel in CO 2 saturated
10% NaCl brine at 80°C, pH 5.65, 1000ppm Fe 2+ with
different concentrations of imidazoline; a) 2D view of pits surface
at 100ppm, b) Cross-section from 2D view pits at 100ppm, c) 3D
view of pits surface at 100ppm, d) Cross-section for x-profile from
2D view at 100ppm, e) 2D view of pits surface at 300ppm,
f) Cross-section for x-profile from 2D view at 300ppm..................... .1 27
Figure 8-1: Corrosion rate versus time for the first 3.5 hours for the step
change process on X65 carbon steel in CO 2 saturated, lOge NaCl
2
brine at 80°C, pH 5.65 and 1000ppm Fe + •.•••••.•••.•.•••••••••.••.•.•••••••...•• ..130
Figure 8-2: Potentiostatic polarisation curve at .f hours to 24 hours on X65

carbon steel in CO 2 saturated, lOge NaCI brine at 80°e. pH 5.65
2
and 1000ppm Fe + without inhibitor.................................................... .131
Figure 8-3: Potentiostatic polarisation curve for 24-hour test on X65 carbon
steel in CO 2 saturated, 10% NaCI brine at 80°C, pH 5.65 and
2
1000ppm Fe + and 1 bar total pressure with different concentrations
of phosphate ester .................................................................................. 132

Figure 8-4: Final potentiostatic current after 24-hour test on X65 carbon
steel in CO 2 saturated, lOge NaCl brine at 80°C, pH 5.65 and
1000ppm Fe 2+ and 1 bar total pressure with different concentrations
of phosphate este~ ................................................................................. 13 2

Figure 8-5: Potentiostatic polarisation curve for 24-hour test on X65 carbon
steel in CO2 saturated, 10% NaCl brine at 80°C, pH 5.65 and
1000ppm Fe 2+ and 1 bar total pressure with different concentrations
of imidazoline......................................................................................... 133
steel in C02 saturated 10% NaCl brine at 80°e. pH 5.65
and 1000ppm Fe 2+ and 1 bar total pressure with different
concentrations of imidazoline ............................................................... 133
Figure 8-7: In-situ image of X65 carbon steel up to 30 minutes in CO 2
saturated lOge NaCl brine at 800 e without inhibitor; a) 1 min.
b) 10 min, c) 20 min. d) 30 min ........................................................... .135
xviii
Figure 8-8: In-situ image of X65 carbon steel in CO 2 saturated 10% )JaCI
brine at 80°C, pH 5.65, 1000ppm Fe 2+ and I bar total pressure
without inhibitor; a) 0.1 h, b) 1 h, c) 2 h, d) 3 h, e) 4 h, f) 5 h........... .135
Figure 8-9: In-situ image of X65 carbon steel in CO 2 saturated 10% .0IaCI
brine at 80°C, pH 5.65, 1000ppm Fe 2+ and 1 bar total pressure
with phosphate ester; a) Blank 1, b) Blank 2, c) 200ppm, d) 100ppm,
e) 50ppm, f) 25ppm, ............................................................................... 136

Figure 8-10: In-situ image of X65 carbon steel in CO 2 saturated 10CJc N aCl
with imidazoline; a) Blank 1, b) Blank 2, c) 200ppm, d) 100ppm,
e) 50ppm, f) 25ppm, ............................................................................... 13 7

Figure 8-11 : Average of maximum pit depth of X65 carbon steel in CO 2
saturated 10% NaCI brine at 80°C, pH 5.65, 1000ppm Fe 2+ and
1 bar total pressure without inhibitor................................................... .138
Figure 8-12: Artificial Pit Depth of X65 carbon steel in CO2 saturated 10CJc
NaCI brine at 80°C, pH 5.65, 1000ppm Fe 2+ and 1 bar total
pressure after test without inhibitors; a) 2D view of pits surface.
b) 3D view of pits surface, c) 3D View of artificial pits surface,
d) 3D view of natural pits surface, e) 2D view of pits surface,
f) 3D view of artificial pits surface...................................................... .139
Figure 8-13: Pit Depth of X65 carbon steel in CO 2 saturated 10% NaCl brine
at 80°C, pH 5.65, 1000ppm Fe 2+ and 1 bar total pressure with
phosphate ester....................................................................................... 140

Figure 8-14: Profilometer image of artificial pit on X65 carbon steel in
CO 2 saturated 10% NaCI brine at 80°C, pH 5.65, 1000ppm Fe 2+
and 1 bar total pressure with phosphate ester inhibitors; a) 2D
view of pits surface at 200ppm, b) 3D view of pits surface at
200ppm, c) 2D view of artificial pits surface at 200ppm , d) 2D
view of natural pits surface at 200ppm, e) 2D view of pits surface
at 25ppm, f) 2D cross-section of artificial pits at 25ppm.................... 141
Figure 8-15: Artificial pit depth of X65 carbon steel in CO 2 saturated 10%
NaCI brine at 80°C, pH 5.65, 1000ppm Fe 2+ and 1 bar total
pressure with imidazoline...................................................................... 1.+2

Figure 8-16: Profilometer image of artificial pit on X65 carbon stee I in
XIX
CO 2 saturated 10% NaCI brine at 80°C, pH 5.65, 1000ppm Fe 2+

and 1 bar total pressure with imidazoline inhibitor; a) 20 \ic\v
of pits surface at 100ppm, b) 30 view of pits surface at 100ppm,
c) 20 view of artificial pits surface at 100ppm, d) 30 view of
artificial pits surface at 100ppm, e) 20 view of pits surface at
200ppm, f) 30 cross-section of artificial pits at 200ppm................... .1.+3
Figure 8-17: FTIR analysis of X65 carbon steel in CO 2 saturated 10% N aCI
after blank test .......................................................................................... 1.+5
Figure 8-18: FTIR analysis of phosphate ester inhibitor in different conditions.... .!46
Figure 8-19: FTIR analysis on the pit site area of X65 carbon steel in CO 2
saturated 10% NaCI brine at 80°C, pH 5.65, 1OOOppm Fe~+ and
1 bar total pressure with phosphate ester in different
concentrations ......................................................................................... 147
Figure 8-20: FTIR analysis on the film area of X65 carbon steel in CO 2
saturated 10% NaCI brine at 80°C, pH 5.65, 1000ppm Fe 2+ and 1
bar total pressure with phosphate ester in different concentrations... .!'+7
Figure 8-21: FTIR analysis of imidazoline inhibitor in difference conditions ........ 148
Figure 8-22: FTIR analysis on the pit site area of X65 carbon steel in CO 2
saturated 10% NaCl brine at 80°C, pH 5.65, 1000ppm Fe 2 + and
1 bar total pressure with imidazoline in different concentrations...... .149
Figure 8-23: FTIR analysis on the film area of X65 carbon steel in CO 2
saturated 10% NaCl brine at 80°C, pH 5.65, 1000ppm Fe 2 + and
1 bar total pressure with phosphate ester in different concentrations
..................................................................................................................150
Figure 9-1: Corrosion rate versus time for the first 2.5 hour on X65 carbon
steel in 10% NaCI brine at 80°C and 10% H2S. 90% CO 2•••••••••••••••••• 15:2
Figure 9-2: Potentiostatic polarisation curve at 4 hour to 24 hour on X65
carbon steel in 10% NaCl brine at 80°C and 10% H~S, 90% CO 2.... ..15:2
Figure 9-3: Corrosion rate versus time for the first 2.5 hours on X65 carbon
steel in 109c NaCl brine at 80°C and lOst H2S, 909c
C02 with nonoxynol-6 phosphate ......................................................... 15:2
Figure 9-4: Potentiostatic polarisation curves for 24 hour tests on X65 carbon
xx
steel in 109c NaCI brine at 80°C and 109c H,S c

- , 90 7c CO,- with
nonoxynol-6 phosphate............................................................................. 154
steel in 10% NaCl brine at 80°C and 100/e H2S, 900/e CO 2
with nonoxynol-6 phosphate ................................................................. 15-1-
Figure 9-6: Corrosion rate versus time for the first 2.5 hours on X65 carbon
steel in 10% NaCI brine at 80°C and 109c H2S, 90% CO 2 with poly
alkyl pyridines........................................................................................ 155
Figure 9-7: Potentiostatic polarisation curves for 24-hour test on X65 carbon
steel in 10% NaCI brine at 80°C and 10% H2S, 90% CO 2 with poly
alkyl pyridine.......................................................................................... 156
steel in 10%NaCI brine at 80°C and 10% H2S, 90% CO 2 with
poly alkyl pyridine ................................................................................. 156
Figure 9-9: In-situ image of X65 carbon up to 60 minutes on X65 carbon
steel in 10% NaCI brine at 80°C and 10% H2S, 90% CO 2 ;
a) 5min, b) lOmin, c) 20min, d) 30rnin, e) 45min, f) 60min.............. )57
Figure 9-10: In-situ image of X65 carbon steel in 10% NaCI brine at 80°C
and 10% H2S, 90% C02 with nonoxynol-6 phosphate; a) 100ppm
at 0.1 h, b) 100ppm at 0.5h, c) 100ppm at 2h, d) 100ppm at
4h, e) 100ppm at 5h, f) 200ppm at 0.lh............................................... .1 58
Figure 9-11: In-situ image of X65 carbon steel in 10% NaCl brine at 80°C
and 10% H2S, 90% CO 2 with poly alkyl pyridine; a) 200ppm at
0.1 h, b) 200ppm at 2h, c) 200ppm at 24h, d) 100ppm at 0.1 h,
e) 100ppm at 0.5h, f) 100ppm at 1h.................................................... )59
Figure 9-12: Artificial pit depth of X65 carbon in 10% NaCl brine at 80°C
and 10% H::,S, 90% CO 2 after the blank test; a) 2D view of pits
surface, b) 3D view of artificial pits surface, c) 2D View of
artificial pits surface, d) Cross-section view x-profile of artificial
pits surface, e) 3D view of artificial pits surface, f) Cross-section
view y-profile of artificial pits surface ................................................ .1 60
Figure 9-13: Pit depth analysis of X65 carbon steel in lOVe NaCl brine at 80°C
and lOVe H2S. 90% CO 2 with different concentrations of
nonoxynol-6 phosphate.......................................................................... 161
xxi
Figure 9-14: 3D image of profi1ometer analysis of artificial pit on X65 carbon

steel in 10% NaCl brine at 80°C and 109c HoS
- , 90% COo- with
nonoxynol-6 phosphate; a) 2D view of pits surface at 100ppm,

b) 3D view of natural pits surface at 100ppm, c) 2D
view of artificial pits surface at 100ppm , d) 3D view of artificial
pits surface at 100ppm, e) 2D view of artificial pits surface at
200ppm, f) 2D cross-section of artificial pits at 200ppm.................... 162
Figure 9-15: Pit depth analysis of X65 carbon steel in 10% NaCl brine at 80°C
and 10% H 2S, 90% CO 2 with different concentrations of poly
alkyl pyridines........................................................................................ 163

Figure 9-16: 3D image of profilometer analysis of artificial pit on X65 carbon
steel in 10% NaCl brine at 80°C and lOo/c H2S, 909c CO 2 with
poly alkyl pyridines; a) 2D view of pits surface at 200ppm,
b) 3D view of natural pits surface at 200ppm, c) 2D view of
artificial pits surface at 200ppm, d) 3D view of artificial pits surface
at 200ppm, e) 2D view of artificial pits surface at 25ppm, f) 2D
cross-section of artificial pits at 25ppm............................................... )64
Figure 9-17: FfIR analysis on X65 carbon steel in 10% N aCl brine at 80°C
and 10% H,S
- , 90% CO..,............................................................................. 166
Figure 9-18: FfIR analysis on Nonoxynol-6 phosphate inhibitor for
different conditions ................................................................................ 167
Figure 9-19: FfIR analysis on the pit site area of X65 carbon steel in
10% NaCl brine at 80°C and 109c H 2S, 90% CO 2 with
different concentrations of nonoxynol-6 phosphate ............................ 168
Figure 9-20: FTIR analysis on the film area of X65 carbon steel in 10% NaCl
brine at 80°C and 10% H 2S, 90% CO 2 with different
concentrations of nonoxynol-6 phosphate.......................................... ..1 68
Figure 9-21: FfIR analysis of poly alkyl pyridines inhibitor in different
conditions ............................................................................................... 171
,
Figure 9-22: FfIR analysis on the pit site area of X65 carbon steel in
109c NaCl brine at 80°C and 10% H2S, 900/c C02 with
different concentrations of poly alkyl pyridines ................................ ..17l
Figure 9-23: FfIR analysis on the film area of X65 carbon steel in 109c NaCl
brine at 80°C and 10% H~S. 900/c CO 2 with different concentrations
XXll
of poly alkyl pyridines ............................................................................ 172

Figure 10-1: Early stage of sweet film formation ....................................................... 175
Figure 10-2: Later stage of sweet film formation ..................................................... .176
Figure 10-3: Sour corrosion film formation............................................................... 178
Figure 10-4: Film formation in sour environments at 90°C..................................... .180
Figure 10-5: FeC0 3 at the outer layer locally isolating the Fe 3C from the
Solution................................................................................................... 185
Figure 10-6: Schematic representation of pitting growth mechanism over time
for X65 carbon steel in CO 2 saturated, 10% NaCI brine at 80°C,
2
pH 5.65 and 1000ppm Fe +, •••••••••••••••••••••••••••••••••••••.••••••••••••••••••••••••••••• 185
Figure 10-7: Schematic representation of pitting growth mechanism over time

for X65 carbon steel in 10% H2S 90% CO 2 , 10% NaCl brine at
80°C and pH 5.65 ................................................................................... 187
Figure 10-8: Effect of underdose of phosphate ester................................................ )89
Figure 10-9: Schematic representation of phosphate ester mechanism
on concentration profile on X65 carbon steel in CO 2
2
saturated 10% NaCl, pH 5.65, 1000ppm Fe + at 80°C ...................... ..190
Figure 10-10: Imidazoline film .................................................................................... .192
Figure 10-11: Schematic representation of imidazoline mechanism
on concentration profile on X65 carbon steel in CO 2
2
saturated 10% NaCI, pH 5.65, 1000ppm Fe + at 80°C ....................... .193
Figure 10-12: In-situ artificial pit surface at start of the test and after 24 hours
in CO 2 saturated 10% NaCl, pH 5.65, 1000ppm Fe 2+ at 80°C........... .196
Figure 10-13: Artificial pit growth mechanism in CO2 saturated 10% NaCl,
2
pH 5.65, 1000ppm Fe + at 80°C for 24 hours.......................... 197
Figure 10-14: Phosphate ester mechanism in CO2 saturated, 10% NaCl,
2
pH 5.65, 1000ppm Fe + at 80°C for 24 hours.......................... 199
Figure 10-15: Imidazoline mechanism in CO 2 saturated, 10% N aCl,
2
pH 5.65, 1000ppm Fe + at 80°C for 24 hours......................... .201
Figure 10-16: Artificial pit growth mechanism in 10% H 2S, 90% CO 2 ,
10% NaCl at 80°C for 24 hours, ........................................................... .203
Figure 10-17: Corrosion rate and pit depth data on concentration profile
for nonoxynol-6 phosphate inhibitor on X65 carbon steeL
lOge H-~S , 90o/e CO~- at 80°C ................................................................... .205
XXlll
Figure 10-18: Nonoxynol-6 phosphate mechanism on X65 carbon steel,

10% H 2S, 90% CO2 at 80°C after 24 hours......................................... .205
Figure 10-19: Corrosion rate and pit depth data on concentration profile for
poly alkyl pyridine inhibitors on X65 carbon steel, 10% H2 S,
900/0 CO 2 at 80°C....................................................................................207
Figure 10-20: Poly alkyl pyridine mechanism on X65 carbon steel, 109'e H2S,
90% CO 2 at 80°C after 24 hours ...........................................................208
Figure 11-1: Inhibitor selection recommendation for localised corrosion
inhibition for oil and gas X65 pipeline field application.................... .214
XXIV
List of Tables
Table 5-1: Chemical analysis in % of carbon steel X65 ________________________________________67
Table 5-2: Corrosion immersion time for sweet tests at 50°C with 1% NaCt ___ }O
Table 5-3: Sour experiment specimens-all specimens pre-corroded in sweet
environment first ____________________________________________________________________________________ 70
Table 5-4: Natural pits blank test specimens at CO 2, 80°C, 10% NaCl,
pH 5 _65, 1000ppm Fe-~+ _______________________________________________ . ___________ ._. ___ ....... } 1
Table 5-5: Natural pit inhibitors test specimens at 150 hours, CO 2, 80°C,
2
10% NaCI, pH 5.65, 1000ppm Fe +........ _________ ..................... _______ ........ }2
Table 5-6: Natural pits test specimens at 10% H2S, 90% CO 2, 80°e,
100/0 N aCl ______ ........... ______________________________________________________________________________73
Table 5-7: Artificial pits inhibitor test specimens at 150 hours, CO 2, 80°C,
10% NaCl, pH 5.65, 1000ppm Fe 2+_____________________________________________________ }4
Table 5-8: Artificial pits inhibitors test specimens at 24 hours at 10% H2S,
90% CO 2, 80°C, I 0% NaCl __________________________________________________________________ }5
Table 6-1: AFM analysis for sweet pre-corrosion specimens _______________________________96
Table 6-2: Relative element composition of sweet pre-corrosion layers _.. __________97
Table 6-3: Relative composition of elements in sour corrosion layers_ ... _.... ________99
Table 6-4: Curve fitting analysis for C Is spectrum __ ._ .. _____ .... _______ ._._. _____ ... __________ .l00
Table 6-5: Curve fitting analysis for Fe 2P3/2 spectrum at 60s _____________________________ .1 03
Table 8-1: FTIR spectra assignments for sweet condition_ ... _. ______ .... _________________ .. .144
Table 8-2: Summary FTIR results for phosphate ester inhibitor at different
concentrations after the test ___________________________________________________________________ 146
Table 8-3: Summary FTIR results for imidazoline inhibitor in different

concentrations after the test ___________________________________________________________________ 149
Table 9-1: FTIR spectra assignments for sour condition_______________________________________ 165
Table 9-2: Summary FTIR results for nonoxynol-6 phosphate inhibitor with
different concentrations _________________________________________________________________________ 167
Table 9-3: Summary FTIR results for poly alkyl pyridines inhibitor at
different concentrations _________________________________________________________________________ 170
Table 10-1: EDX on the sour film at 90°C ______________________________________________________________ .180

Table 10-2: EDX analysis on the sour film at 15°C________________________________________________ .1 8 1
Table 10-3: EDX on the film at 15°C and to 90°C__________________________________________________ .181
xxv
Abbreviations
AP Artificial Pit
ASTM American Society for Testing and Material
AISI American Iron and Steel Institute
AFM Atomic Force Microscopy
BSE Backscattered Electrons
EDX Energy Dispersive X-ray Analysis
Ecorr Free corrosion potential
F Faraday's constant
FTIR Fourier Transform InfraRed spectroscopy
Fm Focused Ion Beam
h Hour
leorr Corrosion current density
mm Minute
NP Natural Pit
OSPAR Convention for the Protection for the Marine Environment of North-
East Atlantic
ppm Parts per million
ppb Parts per billion
pH Level of acidity or alkalinity
Rp Polarization resistance
SEM Scanning Electron Microscope
SE Secondary Electrons
SCE Saturated Calomel Electrode
s Second
T Temperature
V Velocity
XRD X-Ray Diffraction
XPS X-Ray Photoelectron Spectroscopy

Chapter 1 Introduction
1.1 Overview of oilfield corrosion as a global challenge

Carbon dioxide and hydrogen sulphide-related corrosion failures in internal
oil and gas pipelines represent a very serious and costly problem [1-5]. The first
recorded carbon dioxide and hydrogen sulphide corrosion problems were reported in
the United States oil and gas industry in the 1940s [2, 4, 5]. In order to meet the
growth of energy demand, oil and gas exploration moved from shallow water to deep
water and is now moving to super deep water and ultra deep water explorations to
obtain the resources [6]. Furthermore, much of the existing production infrastructure
is operating beyond the original design life and many new locations are being
explored that were previously considered to be out of limits [6, 7J. This creates
significant challenges to operating pipelines in these environments and moreover
transporting the production fluids will require higher reliability and improved
corrosion control, especially in ageing facilities [6, 7]. The advancement in
technology to maintain oil and gas production pipelines is a very attractive economic
strategy and needs proper planning [8, 9]. According to Koch et al. the average
corrosion related cost in the United States of America is estimated to be about $7
billion including monitoring, replacing and maintaining the assets [10]. This corrosion
cost study clearly reveals that the technological advancement demands many new
improved technologies to better understand the corrosion control strategies in
technical and nontechnical areas. Corrosion control requires significant expenditure
while the payoff includes increased public safety, reliable performance, maximised
asset life, environmental protection and more cost effective operations in the long run
[10].
1.2 Carbon steel X65 pipeline operation in oilfield industry

Most pipelines operate under acidic gas environments which in oilfield
terminology, can be regarded as sweet or sour conditions. Reservoir environments
containing measurable amounts of hydrogen sulphide (down to O.5ppm) are classified
as sour conditions and reservoirs free from hydrogen sulphide are classified as sweet
conditions [11]. These acidic gases dissolve in mixtures of hydrocarbons and aqueous
fluids produced from the reservoir [11]. Typically, the operating conditions are more
2
aggressive when these acidic gases di ssolve in the produced fluids that originate from
the geological formation or injected water coming fro m a di stant water inj ec ti on we ll
to maintain the reservoir pressure to sweep oil towards the producti on well , as shown
in Figure 1-1 [12-14]. The produced hydrocarbons and fluid s wi ll be tran smitted from
the offshore platform to the onshore refinery through transmi ssion pipelines mostl y
made from carbon steel X65.
Refinery
Pipeline
Seabed
Figure 1-1: X65 Carbon steel pipeline transporting production fluid from offshore to
onshore facilities.
One of the main failures of this X65 pipeline is through locali sed corrosion
especially pitting and general corrosion problems, as shown in Figure 1-2 [15 , 16].
Weakening of the pipeline by corrosion will reduce the resistance of pipeline to
external forces and will accelerate the materi al and fabrication weaknesse s, which
lead to service failure as a result of leaking, as shown in Figure 1- 3. Most of the
failures are repeated because the pitting mechanism in sweet and sour conditi ons is
not widely understood [6 , 13 , 17 , 18]. Pipe line fai lures due to intern al corrosion can
3
occur in almost any part of the pipeline system and it is imperati ve that the con-os ia n
inhibitor deployed can give good protection to the inside of the entire system [ 19. 20].
Figure 1-2: Locali sed corrosion in pipeline [16]
Figure 1-3 : Leaking in subsea pipeline due to intemal corrosion [16]
Generally , pitting corrosion is difficult to quantify in the fie ld or the laboratory

due to its di screte and random nature . Locali sed corrosion monitoring in oil and gas
production is difficult becau se either larger secti ons of pipeline need to be in spected
or se lected secti ons of a pipeline have to be monitored [2 1] .
1.3 Carbon steel pitting in sweet environments

lntemal pipelin e con-osion processes depend on the service of the pipeline and
operating parameters of the service s [22] . Sweet corro sion services are caused by the
4
presence of carbon dioxide dissolved in the fluids and is also called carbonic acid
corrosion [23]. Major operational parameters that influence sweet corrosion in the
field are pressure, temperature, water cut, water composition, flow rate and the
presence of solids [23]. Carbon dioxide gas is a highly soluble gas compared to other
mineral acids in the sweet system and the acid formed can discharge electrons on the
surface of the metal in several ways [23, 3, 5]. Sweet corrosion can result in a very
high corrosion rate and the mode of attack could often be localised attack [5]. The
surface of the pipe is usually covered with iron carbonate film but local breakdown of
the film can occur and normally the damage is most severe at the bottom of the pipe
where water layers preferentially form [23, 3, 5]. The corrosion control programme at
the facility employs corrosion inhibitors to provide corrosion control to ensure high
productivity [22, 23]. Concerns over the ability of the inhibitor to protect the pipelines
against localised corrosion have been raised as the inhibitor dose is based on general
corrosion. General corrosion is a safe form of corrosion because it is readily
measurable and controlled in the field. However, localised attack results from small
variations in operational conditions and is difficult to locate and measure [23].
1.4 Carbon steel pitting in sour environments

Sour corrosion is caused by hydrogen sulphide in the fluids. Hydrogen
sulphide is a highly toxic and corrosive gas and it is soluble in hydrocarbons and
water [23, 24]. In sour environments, hydrogen sulphide reacts with the surface of the
metal to form adherent iron sulphide films, which are protective but can break down
to reveal bare steel. This breakdown occurs because of the nature of the iron sulphide
film to change its form from initial mackinawite which converts to another sulphide
form and this reaction changes the density of the film and results in cracking of the
film [23, 24]. The bare steel will form a galvanic couple with the iron sulphide film
and can cause rapid pitting attack. Severe localised corrosion can occur in production
pipelines with high hydrogen sulphide content [22, 25]. Such corrosion can cause
failures in a time period as short as a few months if not mitigated [21]. Conversely,
some high sour production systems have not experienced a significant number of
failures due to localised corrosion. This is because of the difference in severity
observed between similar producing systems, which could be due to the presence of
iron sulphides and/or elemental sulphur, which is known to accelerate localised
5
corrosion [21]. In mildly sour systems, the films formed may be a mixture of iron
carbonate and iron sulphide. The protectiveness of iron sulphide film is good but the
stability of the film is generally affected by the salinity, temperature and
metallographic details [22, 23].
1.5 Inhibition of corrosion in oilfield industry

The successful application of X65 carbon steel in oil and gas transmission
pipelines in sweet and sour conditions depends mostly on protective corrosion product
films [26, 27]. Although this film formation can be accelerated by using corrosion
inhibitors it will depend on the operating conditions they are designed to protect.
Often, corrosion inhibitors are used as the solution for avoiding further corrosion
damage but obviously understanding the corrosion mechanism is very important to
resolve the problem [28]. Introducing a new chemical into a field is a complex
process, which involves many operational considerations as well as careful planning
from the conception stage to successful deployment [16]. One important aspect of
overall improvement plans is to initiate a laboratory test programme to evaluate the
new inhibitors, which may offer higher corrosion inhibition performance [29].
Specific test programmes have been designed to study the behaviour of pitting and the
interaction between the inhibitor and pitting corrosion, which is a critical performance
requirement to ensure continuous integrity of the pipelines [16]. Another important
consideration in selecting the inhibitor is the compatibility when mixing with other
chemicals in the system and various operational parameters. With more
environmental regulations, public sensitivity to leakages and significant financial
penalty, this will ensure that more effort is required to achieve the corrosion
management objectives. In order to develop superior corrosion inhibitor products to
better protect different parts of the pipeline system, particularly against pitting
corrosion, a better understanding of the interaction between chemicals and the surface
films is required. Before this can be achieved, a better understanding of the
characteristics of the film formation and pitting process under sweet and sour
conditions is needed.
6
1.6 Objectives of the research

Sweet and sour pitting related failures are a pnme concern In oil and gas
internal pipelines. Often, these types of failure have a great impact on the safety and
environmental matters and can cause severe financial consequences to the operator.
Chemical inhibitors have been used to provide effective protection for the asset
against both localised corrosion and general corrosion. In order to develop superior
localised corrosion inhibitors a better understanding of the mechanisms of the action
and interaction of pitting and the film are required. An extensive study on the
inhibition of pitting corrosion of carbon steel X65 in sweet and sour conditions has
been carried out using electrochemical and post test surface analysis techniques.
The objectives of this study are:

• The development of a laboratory methodology to produce reproducible films
in sweet and sour systems.
• The development of a methodology to initiate and grow pits in a reproducible
manner.
• The investigation of in-situ monitoring techniques to study localised
breakdown.
• The evaluation of the mechanisms of the action and efficiency of localised
corrosion inhibitors.
In order to achieve the objectives of the study, the results section is structured to
comprise four main chapters:
• Investigation of sweet and sour surface film.
• Natural pitting growth in sweet and sour environments.
• In-situ monitoring of pit growth and the effect of inhibition under sweet
conditions.
• In-situ monitoring of pit growth and the effect of inhibition under sour
conditions.
The results obtained in this study show the mechanism of the action of the inhibitor to
withstand pitting corrosion in sweet and sour conditions.
7
1. 7 Scope of work
The scope of work in the first year was to study the methodology to produce
reproducible films in sweet and sour systems and investigate using various surface
analysis techniques to study the generated films. At the same time, the work also
focused on developing an in-situ monitoring technique rig for localised breakdown
and the design of the corrosion sour rig. In the second year, the natural growth of
pitting in sweet and sour environments was investigated and the sweet corrosion
inhibitor performance was evaluated on natural pits. In the third year, the corrosion
inhibitor performance was evaluated on artificial pits with in-situ monitoring
techniques in sweet and sour environments and ex-situ FTIR analysis.
1.8 Outline of the thesis

The thesis is presented in eleven chapters:
Chapter 2 is the basic theory of corrosion discussing electrochemical reaction,
the kinetics and thermodynamics of corrosion and classification of type of corrosion
with emphasis on pitting corrosion.
Chapter 3 presents the review of the literature on corrosion in sweet and sour
environments. The reviews are related to mechanism, corrosion films, operating
parameters and a summary of current research status with a focus on pitting corrosion.
The review also covers the development of in-situ techniques, artificial pit and surface
analysis techniques.
Chapter 4 presents the design and development of the in-situ monitoring rig
and sour rig. This also covers the safety and operational procedure to operate the sour
fIg.
Chapter 5 presents the experimental techniques describing the sample

preparation, techniques, experimental rigs, methods and procedures used in this study.
The post-test examination is also explained in this chapter.
8
Chapter 6 presents the experimental results from the investigation on sweet

and sour surface films. The corrosion film is generated and the film is further
investigated using various surface analysis techniques.
Chapter 7 presents the experimental results from natural pit studies in sweet
and sour conditions. The pits are generated and the pit depth measurements are
obtained by post-test analysis with surface profilometry. Sweet corrosion inhibitors
are also evaluated on natural pits.
Chapter 8 presents the experimental results from the in-situ monitoring

technique on artificial pits under sweet conditions. The sweet corrosion inhibitor is
evaluated and the pit depth measurement is obtained by post-test analysis with a
surface profilometry. Further FTIR analysis is also carried out to investigate the
corrosion inhibitor mechanisms.
Chapter 9 presents the experimental results from the in-situ monitoring

technique on artificial pits under sour conditions. The sour corrosion inhibitor is
evaluated and the pit depth measurement is obtained by post-test analysis with a
surface profilometry. Further FTIR analysis is also carried out to investigate the
corrosion inhibitor mechanism.
Chapter 10 presents a detailed discussion of the experimental results,

comparing the work in this thesis with other reports in the literature and establishing
the differences and contributions of this study. The principal sections in this chapter
relate to sweet and sour film investigation and the effects associated with the film
protectiveness and film breakdown. This chapter also discusses the formation of
pitting in sweet and sour corrosion from the perspective of pitting depth and the effect
on corrosion rate. Moreover it also discusses the individual inhibitor component
mechanisms on the film and pitting area in sweet and sour environments.
Chapter 11 presents the conclusions made from the study and focuses on the
contribution of the current work to the existing knowledge. This chapter also suggests
the industrial applications of this work and future work for further understanding of
pitting corrosion inhibitor mechanisms.
9
Chapter 2 Fundamental theory
2.1 Corrosion
Corrosion is the degradation of a material through the reaction with its
environment [5, 14, 30-36]. Corrosion is subdivided into dry, wet and hot type
corrosion for metals and non-metals. The process of corrosion occurs at the surface of
the material, which is destructive or beneficial for the material depending on its
application [31]. The science and art of corrosion engineering are intended to control
or prevent corrosion damage on the material economically and safely [30, 32].
2.2 Electrochemical reactions of aqueous corrosion

Aqueous corrosion is the reaction of the material at the interface with the
electrolyte of the material where the anodic dissolution and the cathodic reduction
take place, which is the domain of metallurgists and physicists [31. 32]. The anodic
reaction or oxidation involves a loss of electron metal by an increase in valence [30,
33]. Simultaneously, a cathodic reaction or reduction process decreased in valence
charge consumes the electrons generated from the anodic process. This leads to the
basic corrosion principle, which states that the rate of oxidation is equal to the rate of
reduction. All parts of a metal surface during the corrosion process are anodic and
cathodic alternately over a period of time in which both reactions are mutually
dependent upon each other [30, 33, 34].
The anodic and cathodic reaction when iron is immersed in water or seawater
with the presence of oxygen is as follows [30]:
Fe -+ Fe 2+ + 2e 2-1
2-2
Sodium and chloride ions in the solution do not participate in the reaction, which
makes the overall reaction as:
2-3
10
Ferrous hydroxide precipitated from the solution is unstable in an oxygenated solution

and is oxidised to ferric salt, which makes the final product of familiar rust [30]:
2-4
2.3 Thermodynamics of corrosion reactions

The thermodynamics of corrosion are influenced by the chemical and
electrochemical processes of the surface and interfacial energy of the material [31, 32,
34, 35]. The energy of the reaction is described by the change in their internal energy
or enthalpy. The equilibrium electrode potential when concentrations of all reactions
are maintained at unit activity are termed as half-cell standard potentials [30]. In any
electrochemical reaction, the most negative or active half-cell tends to be oxidised and
the most positive or noble half-cell tends to be reduced [31, 32, 34, 35]. The potential
difference can be measured with a reference electrode quoted on a scale relating to the
electrode. The potential difference between two reactions arises from the
thermodynamics of the electrode reaction involved [31, 32]. The equilibrium
potentials of an electrode reaction may include the formation of protecting insoluble
salts or other compounds, which may also lead to corrosion protection. The reduction
will proceed until the potentials of the two reactions are equal [31, 32, 35]. In order to
account for all the likely corrosion phenomena, it is necessary to know what products
are possible [31].
2.4 Free energy

The change in free energy L1G is a measurement of the work capacity available
from a system. A negative change in free energy accompanying the transition of a
system from one state to another indicates a loss in free energy and also the
spontaneous reaction direction of the system [30-33]. The system will transform to its
lowest energy state if no external forces act on it. A positive change in free energy
indicates that the transition represents an increase in energy and requires the addition
of energy to the system. The change in free energy is a state function and independent
of the reaction path [30, 31].
11
2.5 Kinetics of corrosion reactions

In order to produce a change in the electrode reaction so that the current
density in one direction is greater than in the other direction, the potential of the
electrode must change from the equilibrium value [30-32]. The change is referred to
as polarisation. The relationship between the change and the value of the net current
density is represented by a polarisation curve. The shape of polarisation cur\'e is
composed of three separate effects: activation polarisation requirements.
concentration effects and resistance effects [30].
2.6 Polarisation
Polarisation can be defined as the displacement of electrode potential resulting
from a net current or the deviation from equilibrium potential [30]. Electrochemical
polarisation is divided into two different types: activation polarisation and
concentration polarisation [30-36]. Activation polarisation refers to an
electrochemical process controlled by the reaction sequence at the metal-electrode
interface. This is the process of reduction of any species on a metal surface [30-33].
The absorbed or attached species on the surface will transfer the electron resulting in a
reduction of the species. Concentration polarisation refers to electrochemical reactions
controlled by the diffusion in the electrolyte [30, 31]. Concentration polarisation
generally predominates when the concentration of the reducible species is small [30,
31]. At low reaction rates, activation polarisation usually controls whereas at higher
reaction rate, concentration polarisation becomes controlling, as shown in Figure 2-1.
o
fJr
ConC8fltration
polarization
Log i
Figure 2-1: Combined polarisation curve-activation and concentration polarisation

[30].
12
The behaviour of the metal can be divided into three main regions: active.
passive and transpassive, as shown in Figure 2-2 [30]. In the active region, the
material behaviour will be identical to that of a normal metal. A slight increase in the
oxidising power of the solution causes a rapid increase in corrosion rate [30, 31]. This
process will lead to the addition of oxidising agents added and a sudden decrease in
corrosion rate corresponding to the beginning of a passive region. With increasing
oxidising power, a very high concentration of oxidisers will reach a stage where the
corrosion rate will increase again. At this stage the behaviour of the metal reaches a
transpassive region [30-33].
Transpassive
t
Solution
oxidizing
--- --- ---- -----Ipass;""
-----
power
(electrode
potential) Active
10 100 1000 ·0000

Corrosior rate
Figure 2-2: Corrosion characteristics of active-passive metal as a function of the
solution oxidising power (electrode potential) [30].
2.7 Mixed potential electrodes

In mixed potential theory, any electrochemical reaction can be divided into
two or more partial oxidation and reduction reactions and there can be no net
accumulation of electric change during an electrochemical reaction [30, 31]. A mixed
electrode is an electrode or metal sample in contact with two or more oxidation-
reduction systems. The corrosion behaviour of iron in dilute hydrochloric acid
solution represents two reactions, which are iron dissolution and hydrogen evolution,
as shown in Figure 2-3 [30].
13
+0.2
-0.0
-", -0 .2
I
<n
:.
- - - - - -E.;,~
- -~"- - -
W -0 .4
-0 .6
10' 0 10 .8 0 -6 0'"
Curr t density . amp/em '
Figure 2-3: Schematic representation of electrode kinetic behaviour of pure Iron In
acid solution [30].
2.8 DC Linear polarisation test method

The mixed potential theory forms the basis for linear polari sation techniques
to determine the corrosion rate . Figure 2-4 show s a typical three electrode cell
submerged in an electrolyte for electrochemical corrosion tests. The potenti ostat shifts
the OCP of the working electrode and measure the respective current [36] . Changing
an electrode potential from its OCP is referred to as polarization [36] .
Power
Potentiostat
Supply
~,_--+- Electrome ter

Ammeter ---l-~
Test
Electrode
Counter _-+_
Electrode
......._ _ Reference
Electrode
Figure 2-4: Three electrode test ce ll sc hem atic [36] .

14
Within 10m V more noble or more active than the corrosion potential, it is
observed that the applied current density is a linear function of electrode potential [30,
36]. The corrosion potential is used as an overvoltage reference point. The plot of
overvoltage versus applied anodic and cathodic current is shown on a linear scale, as
in Figure 2-5. The plot represents the first 20m V linear polarisation of the curve
related to the kinetic parameters of the system, as in [30, 36] where ~a and ~c are tafel
slopes of the anodic and cathodic reactions, respectively, and term ~E/!'1i is given in
n.cm 2 . Stem and Geary developed a mathematical relationship between corrosion
resistance and corrosion current for linear polarisation, as follows [30, 36].
2-5
The slope of a linear polarisation curve /'1E/!'1i is controlled mainly by icorr and
is relatively insensitive to a change in beta value. An error in obtaining the correct
beta value from the tafel slope could affect the icorr value. The beta value should be
taken from the test electrode that is in a steady state and compensated for the solution
resistance [30]. In this study, localised corrosion kinetics and solution chemistry could
have an effect on obtaining an accurate beta value for the experiments. By assuming
the worst case scenario, an anodic and cathodic beta value of 0.12 volts is chosen to
represent the average of all corrosion systems, which may be used to calculate the
corrosion rate in this study by simplified equation [30, 36].
t:.E 0.026 2-6
Corrosion rate can be converted to MPY by the following equation [36]
2-7
Where:
5
A IS a combination of several converSIOn terms 1.2866 xl0
(equivalents .sec .mils/Coulombs.cm.years)

Icorr is corrosion current density Amps/cm2 (I Amp = I Coulomb/sec)
15
P is iron density 7 .86 g/ cm 3
E is equi val ent weight for iron 27. 56g/equ ivalent
C orrosion rate can be converted from MPY to mrnlyr using the following equ ati on
mm/yr = MPY x 0.0254 2-8
T)(mv)
/
20 /
I
/
I-
10
40 20 40
-- I~PP(C otho<j,cl ' o pptonOd l(1 ~
-10
7
'/
I
/
/ -20
/
Figure 2-5 : Applied-current linear polari sati on curve. [30]
2.9 Type of corrosion
2.9.1 General corrosion

General corrosion or uniform attac k is the most common fo rm of corrosion. It
can be characteri sed by a chemical or electrochemical reaction that proceeds
uniforml y over the entire exposed surface or over a large area [30-36]. The fai lure of
the uniform corros ion can be identified by metal loss and the meta l becoming thinner
and eventually failing. The life of the equipment can be acc urately estimated on the
basis of a comparati ve ly sample test [30- 36].
2.9.2 Galvanic corrosion

Galvani c corrosion may happen when two diss imil ar metals are invo lved and
are In contac t and immersed in an aqueou s environment [30, 32]. The potenti al
differe nce between them wi ll ini tiate attac k on the less nobl e of the two metal at a
16
corrosion rate largely dependent upon the surface reactions of the two metals. The less
resistant metal becomes anodic and the more resistant metal becomes cathodic,
usually the cathodic metal corrodes very little or not at all in this type of coupling [30.
32].
2.9.3 Crevice corrosion

Crevice corrosion or deposit corrosion IS an intensive localised corrOSIOn
occurring within crevices and other shielded areas on a metal surface exposed to a
corrosive medium [30-36]. This type of attack is related to small volumes of stagnant
solution in which the excess of the working fluid is limited, and is usually caused by
holes, gaps, lap joints and surface deposits [30, 32]. Deposits that may produce
crevice corrosion are usually sand, dirt, corrosion products and other solids, which act
as a shield and create a stagnant condition under them [30, 32].
2.9.4 Intergranular corrosion

Intergranu1ar corrosion is related to grain boundary effects in which the grain
interfaces are very reactive, which causes a localised attack at and adjacent to the
grain boundaries with relatively little corrosion of the grains [30, 32]. This can come
from impurities at the grain boundaries, enrichment of one of the alloying elements or
depletion of one of these elements in the grain boundaries area, which can cause a loss
of strength [30].
2.10 Pitting corrosion

Most of the corrosion phenomena are related to the formation of a film on the
surface of the metal [5, 20, 30, 31, 37]. Under certain conditions, these film passivity
layers may be destroyed locally, which leads to special corrosion phenomena like
pitting corrosion, crevice corrosion and stress corrosion craking [31]. Pitting is a form
of extremely localised attack resulting in small or large diameter holes or cavities in
the metal with the surface diameter about the same as or less than the depth [30, 31,
37].
17
2.10.1 Mechanisms of pitting corrosion

Pits initiate when the rate of metal dissolution is momentarily high at one
particular point and the chloride ions will migrate to this point. The presence of
aggressive anions within the electrolyte cause localised attack on most passivated
metals and alloys leading to the formation and growth of corrosion pits [30, 31].
Initiation or the early growth stage of pits results in rather unstable conditions due to
repassivation. Most pitting failure is caused by chloride and chloride containing ions,
which increase the metal dissolution. The adsorption of cr through a passive film
surface to the metal/oxide interface causes the build up of metal chloride at the
interface, leading to film thinning [30, 31]. The adsorption, complexation and
thinning of the passive film lead to a complete breakdown of the film, as shown in
Figure 2-6 [30, 31]. Chloride ions are adsorbed on the oxide surface and form a
complex with the surface cations. High solubility of the complex would enhance the
dissolution and cause a local thinning of the passive film, which then leads to local
depassivation and film breakdown [30, 31].
passive film electrolyte

metal
(2 - 10 nm)
(//
.. '
electrolyte with
aggressive ions
>. ..
'.
pit growth ...............

competition
passive film ~ chloride film
(aggressive anions)
Figure 2-6: Mechanisms of film breakdown [31]
The presence of chloride could prevent repassivation of locally depassivated

surfaces and, ultimately, causes pitting [31]. Dissolution will increase because of
mechanical stress at a defect or random variation in the composition of the solution.
Pitting is more likely to occur on etched or ground surfaces than on polished surfaces
but pits forming on a polished surface are larger and penetrate more rapidly than those
on a rough surface [30, 31].
18
2.10.2 Pitting shape and growth

Most pitting develops and grows downward from a horizontal surface, usually
in the direction of gravity. The dense concentrated solution within a pit is necessary
for its continuing activity and is a direct result of the autocatalytic nature of pitting
[30, 37]. Pits often start with a small polygonal form and change to a hemispherical
form when the precipitation of corrosion products occurs [31]. The surface of
hemispherical pits may be rough depending on the formation of low solubility
deposits during their growth [31, 37].
2.10.3 Evaluation of pitting damage

Pits are difficult to measure quantitatively and compare because of the varying
depth, size and number of pits that may occur. The conventional weight loss test
cannot be used for evaluation or comparison because the metal loss is very small and
does not indicate the depth of penetration [30, 38]. The measurement of maximum pit
depth as a function of exposed area would be a more reliable way of expressing
pitting corrosion, since it is the deepest pits that will cause failure [30, 37].
2.11 Corrosion inhibitors

Corrosion inhibitors are a class of chemical substances that decrease the
corrosion rate when present in the corrosion system in sufficient concentration
without significantly changing the concentration of any other corrosive agents [31,
39]. The inhibitor can modify the surface layer by precipitation, pore plugging and
enhanced film growth by the corrosion potential remaining unchanged and decreasing
the corrosion rate [31]. Some surface active agents may act as inhibitors by providing
an inhibition due to film formation and adsorption on the metal surface, interface or
on the porous corrosion layer [31, 40]. Various types of corrosion inhibitor have been
used for different applications. Generally, corrosion inhibitors can be classified as
[31] :
Anodic, cathodic and mixed inhibitors
Organic and inorganic inhibitors
Oxidising and non-oxidising inhibitors
Interface (2D) and interphase (3D) inhibitors, according to thickness of
formed layer
19
Oil field, cooling water, de scaling and acid cleaning inhibitors.
Inhibitors may act on both cathodic and anodic partial electrode reaction. The
cathodic inhibitor shifts the corrosion potential in the negative direction and forms an
insulating layer, while the anodic inhibitor causes a change in the positive direction
and forms a passive layer [31, 40]. Some mixed type inhibitors provide protection by
blocking the whole surface and control the charge transfer or mass transport on the
surface [30, 31, 40].
20
Chapter 3 Literature review
3.1 Sweet corrosion in carbon steel

The successful application of X65 carbon steel in oil and gas transmission
pipelines in sweet and sour conditions depends mostly on the production of a
protective corrosion product film [41-43]. The wide variety of operational
environments and production fluids present vast challenges to operators to maintain
transmission pipelines. Carbon dioxide is usually present in the fluid produced, which
is a highly mineralised medium containing ions of chloride, carbonate, bicarbonate,
sulphide, calcium, magnesium, sodium, potassium and iron [11, 14]. The presence of
this element in its aqueous phase can result in very high corrosion rates in which the
attack often leads to localised corrosion [5, 44]. Carbon dioxide corrosion in oil and
gas pipelines is effected by a number of factors including supersaturation,
temperature, solution pH, carbon dioxide partial pressure and sweet corrosion film [3,
5,44-48].
3.1.1 Electrochemistry of sweet corrosion

Carbon dioxide gas is not corrosive by itself at normal temperatures but
corrosive if dissolved in the aqueous phase [5]. Carbon dioxide gas dissolved in water
generates carbonic acid [5, 13, 29, 47- 50].
3-1
The anodic dissolution for the iron in acid solution [2, 29, 47-49]:
Anodic reaction:
Fe ---+ F e +2 + 2-
e 3-2
The cathodic process of mild steel in the solution is dominated by the diffusion of
hydrogen ion reduction at pH 2 - 4 and the reduction of HCO~ and H2 C0 3 becomes
important when the pH increases to pH 4 -7 [5, 29,45,47-49.51]:

21
Cathodic reactions:
At a lower pH
2H+ + 2e- ~ H2 3-3
At a higher pH
2H 2C0 3 + 2e- ~ H 2 + 2HCO~ 3-4
2 HCO~ + 2e- ~ H 2 + 2 CO~ 3-5

Direct reduction of water
3-6
2
When the concentration of Fe + and CO~- ion exceed the solubility limit of solid iron
carbonate precipitates the formation of the carbonate film takes place [29,47,48,49,
50,51].
Fe 2++ CO~- ~ FeC0 3 3-7
Fe + + 2 HCO~ ~ Fe(HC0 3h
2
3-8
Fe(HC0 3 h ~ FeC0 3 + CO 2 + H 2 0 3-9
The electrochemical reaction would deposit a corrosion scale on the surface of the
carbon steel which can be protective or non-protective depending on the
microstructure and characteristics of the film [3, 5,13,29,49,50].
3.1.2 Effect of supersaturation

Supersaturation plays an important role in the formation and stability of iron
carbonate film. High supersaturation accelerates the film formation and improves the
stability and protectiveness of the film [5, 49, 52, 53]. High supersaturation of Fe 2+
and CO~-, which are released from the steel surface by corrosion and those coming
from bulk solution, form an iron carbonate layer on the carbon steel surface [47. 52-
54]. High supersaturation can be generated by increasing the bicarbonate and iron
concentration to accelerate the film formation process [20]. Nesic et al. found that the
higher Fe 2+ concentration plays an important role in reducing the corrosion rate, as
22
shown in Figure 3-1 [20]. At high supersaturation, the corrosion rate has less effect on
the corrosion layer accumulation rate of iron carbonate [50]. High supersaturation
cannot be sustained for a long time at high temperature, as accelerated precipitation
will tend to rapidly revert to a thermodynamic equilibrium [3]. At low
supersaturation, which is typical for field conditions, the corrosion layer accumulation
rate for iron carbonate is strongly affected by the corrosion rate of steel [47,55,56].
2.5
1
~ I
E 21\--:,-'-~~--------_ 5 ppm
£ i\\
2 1.Sj \ \
ca I" 2.5 ppm
II
ell
1\ '.100ppm
\
.~ ~ '.
e :\ \
8 0.5~ \ ~
o 250 p p K - - - - - -
1
o 5 10 15 20 25 30 35
Time (h)
2
Figure 3-1: Predicted effect of Fe + concentration on the corrosion rate for T = 80°C,
pH 6.6, PC02=0.54 bar and V = lmls [20]
3.1.3 Effect of temperature

Temperature accelerates all the processes m corrOSIOn involving
electrochemistry, chemical and transportation [3, 57, 58]. The change of temperature
is important to film stability because it may affect the solubility and change the
behaviour of the film [5, 59]. An increase in temperature also leads to increased
supersaturation by rapidly accelerating the kinetics of precipitation to form a
protective film to reduce the corrosion rate [3, 5, 58]. At temperatures higher than
60°C, the solubility of iron carbonate in the solution decreases and high
supersaturation can lead to high precipitation [3, 5]. The temperature strongly affects
the characteristics and morphology of the film by improving the protectiveness, which
virtually reduces the film porosity and increases the adhesion and hardness of the film
[5]. Iron carbonate is more stable at a temperature of 60°C - 90°C and becomes
denser, and therefore, more protective over time [49, 59]. Figure 3-2 shows that the
increase in temperature accelerates the formation of the protective film process, and,
therefore, increases the surface coverage due to the higher precipitation rate [20, -+9].
An iron carbonate film will also form at low temperature if the pH and dissolved iron
23
carbonate concentration in bulk is high [5, 54]. However at a lower pH. increasing the
temperature will increase the corrosion rate due to the precipitation of non-protectiye
films, which have a porous structure [5].
2.5'1- - - - - - - - - - - -...- ---
55°C
o 5 10 15 20 25 30 35
Time (h)
Figure 3-2: Predicted effect of temperature on the corrOSIOn rate for pH 6.6,
Pc02 =0.54 bar, C Fe2 + = 250ppm, and V = 1m/s [20]
3.1.4 Influence of pH
The solution pH plays an important role thereby affecting supersaturation,
which influences the formation of a protective film and has a direct effect on the
corrosion rate [3, 5]. Increasing the pH favours high supersaturation, which in tum,
increases the film's precipitation rate [12,41,53]. Increasing the pH will reduce the
solubility of the Fe 2 + product, which leads to the probability of generating a protective
2
iron carbonate film. As an example, at pH 4 - 5 the solubility of Fe + reduces 5 times
2
and is even lower at a higher pH 5 - 6, which reduces the solubility of Fe + by 100
times [5, 17,41].
The pH of saturated carbon dioxide condensed water is typically around pH 4

or less [3]. Figure 3-3 shows that the corrosion rate reduces when the pH increases to
pH 6.6 [20]. The cathodic reaction dominates by H+ reduction at low pH < 4.5 and
HCO~ and H2C03 control cathodic reaction at pH > 5, which lead to more protective
films [19,41,51].
24
2.5'1- - - - - - - - - - -
I
>- I
E 2j
E
~ ttl~---=::::::::_--------~pH 5.8
21.51
C1l I
ie 1j
....
I
I
\
\
\H626
pH 6.0
8°·5: I
pH 6.6
I
O~i--~~~==~~~~~==~--~
° 5 1 15 ° 20
Time (h)
25 30 35
Figure 3-3: Predicted effect of pH on the corrosion rate for T=80°C, Pc02 =0.54 bar,
C Fe2+ = 250ppm, and V = 1rnfs [20]
3.1.5 Influence of carbon dioxide pressure

Carbon dioxide partial pressure will increase the carbon dioxide corrosion rate
in the absence of a protective film [3]. However, when the conditions are favourable
for the formation of a protective film, higher carbon dioxide partial pressure will lead
to an increase in bicarbonate and carbonate ion concentration [20]. This condition will
lead to higher supersaturation, which accelerates precipitation and film formation [3,
44].
3.2 Sweet corrosion films

There are many types of surface film that form on carbon steel during the
carbon dioxide corrosion process. They can generally be divided into four main
classes - transparent films, iron carbide films, iron carbonate films and iron carbonate
plus iron carbide films [2, 3, 5,29]. All these films are different in thickness, structure
and morphology, which lead to different corrosion rates and levels of protectiveness
[5,46,60].
The precipitation kinetics of the film influences the nucleation and particle
growth of the film. The protectiveness of the film will increase with exposure time
and once the film formed is protective, it will remain protective even at lower
supersaturation [5]. The protective film may be weakened by high chloride
concentrations and by the presence of organic acid due to the reduction in the film's
stability [41, 44, 56, 57].
25
The formation and protectiveness of the film also depends on the

characteristics of the carbon steel microstructure, heat treatment and alloying element
contents [5, 13, 48, 61, 62, 63]. The differences are mainly because of the build-up of
carbide on the corroded steel surface, which can increase the corrosion rate due to
galvanic corrosion between bare metal and Fe3C [5, 29]. The anchoring effect of the
carbide phase is also the main factor influencing the adhesion of the iron carbonate
film structure [29, 64]. The pearlitic/ferrite microstructure has a carbide structure,
which provides a good framework for the build up of protective carbonate film,
however, the quenched and tempered steel and ferritic steel with low carbon content
does not offer the integrated framework due to the finely distributed carbide structure
[5,48,62-64].
3.2.1 Transparent films

Transparent film is a class of protective film that can form with very low
ferrous ion concentration but is not considered as a thermodynamically stable solid
carbon dioxide corrosion product. This film, with less then 111m thickness, can only
be observed at room temperature and will form faster by reducing the temperature
below the ambient temperature [5]. Auger electron spectroscopy shows that the rough
proportion of iron to oxygen ion in the film is 1:2 and does not show any carbonate
[5].
3.2.2 Iron carbonate film

When the concentration of Fe 2+ and CO ~- ions exceeds the solubility limits,
iron carbonate precipitation take places on the surface of the material [47, 54]. Iron
carbonate slows down the corrosion process by covering the metal surface and, thus,
creates a diffusion barrier for the species involved in the corrosion process [3, 47, 65].
The protectiveness of iron carbonate films depends primarily on the precipitation rate
of the film and the corrosion rate of the steel. Whether a protective film forms or not
depends on the structure and morphology of the film and the thermodynamics and
kinetics of the corrosion process [5]. A dense and protective film forms if the
precipitation rate of the film exceeds the corrosion rate [3, 29].
26
3.2.3 Iron carbide film

Iron carbide is another species that can be generated on the surface under
carbon dioxide environments [3, 5, 29, 64]. The corrosion process from the surface
enriches the iron carbide in the film. Fe3C is left behind from the corrosion process
and differs from the formation of the FeC0 3 corrosion product layers [29]. Fe3C is
generally not effective in reducing the corrosion rate due to the film structure and
morphology of the layers [5, 29, 64]. Fe3C layers generally have poor contact and
bonding at metal surfaces with some unfilled regions between the surfaces. This
structure makes the surface fragile and porous which leads to its unprotective nature
[5,29].
3.2.4 Iron carbonate plus iron carbide film

Mixed iron carbonate and iron carbide film is the most common film found in
carbon dioxide corrosion on the surface of carbon steel. The structure and
protectiveness of the film is dependent on the iron carbonate film precipitations, as
shown in Figure 3-4 [29]. The corrosion film appears to contain a double layer as
iron carbonate film grows on the surface and the steel surface corrodes under the film
continuously creating a void between the film and the surface, which is called the film
undermining [20, 29, 51]. The void will then be filled with ongoing precipitation as
soon as the void is created. Dense and protective films will form if the rate of
precipitation at the steel surface equals or exceeds the rate of corrosion undermining.
However, a porous and unprotective film will be created if the rate of corrosion
undermining is faster than the precipitation that can fill the voids [13, 20, 29].
This process will generate three types of films, which are fully protective film,
semi protective film and unprotective film, depending on the corrosion process that
takes place [64]. The film can also change with time until it becomes a fully
protective film to reduce the corrosion rate [64]. The protective film is sometimes
very thin but still protective, and, vice versa, the film can be very thick but
unprotective [20]. Figure 3-5 shows the dense and porous layer of film on the steel
surface [3, 29].
27
anp otec ive
Fe~ FeCo,
Pr otective
~c FeCO
Me ill Me'al
Figure 3-4: Morphologies observed for protective and unprotective cOlTosion layers
[29]
Figure 3-5: SEM image of a cross section of a steel specimen including iron carbonate
scale. Exposed for 10h at T=80°C , pH = 5.6 , Pc02 =0 .54 bar, C Fe2 + = 250 ppm , and V =
1 mls [20]
28
3.3 Sweet pitting corrosion on carbon steel

Carbon Steel X65 pipelines used in the oil and gas industry are frequently out
of service due to localised corrosion attack and most of the failures cannot be fully
explained by applying the principle of localised corrosion on stainless steel [17, 66,
67]. During the oil and gas transportation, water is separated and concentrates in the
lower part of the pipeline, which makes that area the hot spot of localised corrosion
[68]. Three types of localised corrosion are generally detected in carbon steel
pipelines of which the most severe is pitting corrosion, followed by crevice corrosion
and mesa attack [5, 44, 66]. Most of the carbon steel pipeline failures have a low
general corrosion rate down to less then O.lmmJyr but less than scale pitting defects
[9].
3.3.1 Pitting corrosion failure

Pitting corrosion can occur over the full range of operating conditions - under
stagnant to moderate flow conditions [5, 44, 67]. Pitting corrosion initiates due to the
transient change in the environmental conditions like an increase in chloride IOn
concentration, temperature and partial pressure of CO 2 [41, 69-71]. Chloride IOn
content is important in localised corrosion because it largely affects the ionic strength
and, thus, the supersaturation level of the solution [11, 17, 56, 67]. Temperature is
another parameter that influences the pitting process; generally, most of the pitting is
G
likely to occur in sweet pipelines at a temperature range of 70 - 90 C [48].
The surface finish and microstructure of carbon steel can also influence the
pitting process. A rougher surface generally provides more occluded geometries
around sites, which can be the pit initiation sites, especially metastable pits [72]. Pits
are likely to initiate at metallurgical discontinuities in the steel such as grain
boundaries, pearlitic colonies and banded phases [73].
The pitting corrOSIOn process for stainless steel can be divided into three
sequences or steps - initiation by breakdown of passive film, initiation by metastable
pits growth and stable growth pits [74]. The pits distribution is generally composed of
three main populations, which are very small pits mainly dead pits or pits that are late
29
to initiate; pits that are formed from metastable pitting and pits that are formed by
super stable pitting [75].
3.3.2 Pit initiation in sweet conditions

The initiation stage of pitting starts with the breakdown of iron carbonate films
that largely depend on the undissolved cementite layer in the film morphology [62].
When there are flaws in the iron carbonate film content, or it is porous or has other
imperfections located at the interface between the base material and scale, it will
result in further destruction in the local cells at the site followed by localised attack
[62, 63]. This will develop an aggressive local chemistry at the corroding site, which
leads to cracking the iron carbonate layer [5,54,63, 72, 74].
Galvanic coupling between the steel and undissolved iron carbide layer
provides local acidification in the aqueous solution that is trapped within the porous
film [29]. This leads to a situation where a temporary local anode appears and
unbalances the local equality between the anodic and cathodic current [29]. The
corresponding reaction would enhance the protectiveness of the deposit formed and
leads to the random nature of the pits nucleation [29]. Most of the film failure
coincides with the underlying pit, where the pits grow under the porous corrosion film
due to local cell mechanism [5, 8, 76, 77].
3.3.3 Metastable pits

The pitting nucleation stage is a very quick process and can occur within a
very short time of exposure [70, 78]. The presence of a cover or salt film cover of the
pits was found, which helps to maintain the aggressive local chemistry within the pits
[72, 79, 80]. The pit cover will eventually collapse and the pit must be in an
environment that favours propagation in order to become a stable pit, however,
metastable pits are unlikely to become extreme and may terminate the growth whilst
still in metastable pits [72, 74, 78,81]. The pit growth is a self sustained process and
would also contribute to hinder the dissolution at the bottom of the pit as a result of
Fee 0 3 precipitation. The pit may also grow spherically until a certain radius,
followed by the opening of the pit mouth and lateral growth [28, 82]. The pit may
continue to grow sufficiently large and sometimes the growth rate will accelerate the
30
autocatalytic process; the final pit depth depends on the pit growth rate and its
initiation timing [15]. The pit may grow in various sizes and shapes, as shown in
Figure 3-6; however, the true depth is the main parameter that leads to failure [22,
38].
. . t:::=s 'I,
Figure 3-6: Variations in the cross-sectional shape of pits [38]
3.3.4 Stable pits

Pits that continue to grow can be quite large when the pit depth provides the
boundary depth necessary for diffusion control [78]. The rapid growth of a uniform
pit cover layer decreases the pH inside pits, which might be as low as zero, and,
which is attributed to the increase in chloride concentration to reach the saturated
level inside the pits [17,79,83]. Once the pit is engaged in stable growth. the local
chemistry inside the pits becomes more corrosive and the bulk solution and solution
within the pits become acidic and have a high concentration of Fe 2+ and cr [68, 79,
83]. The salt film covering the pit helps to maintain the harsh conditions inside the pit
and limits access to the pitting surface by surfactant molecules [72, 79]. This harsh
condition makes it difficult to stop the dissolution of supersaturation compared with
the conditions when the pits are at the initiation stage [72, 79, 84].
31
3.3.5 Pit propagation in sweet environments

Pit propagation under CO 2 corrosion is mainly influenced by the difference
between the iron carbonate film and the bare steel surface [50, 15, 85. 86]. Pits that
grow underneath a corrosion product layer made up predominantly from iron
carbonate may start the growth with small pits and merge with neighbouring pits to
form larger pits [50]. Stable pit propagation will occur when a stable difference in
corrosion potential is established between the anode and the cathode and the condition
is close to saturation with respect to iron carbonate film when no dissolution or
precipitation is expected [50, 86]. Solution conditions need to be maintained at a
favourable condition in order for the pits to continue to propagate [50, 85]. One of the
key factors that determine propagation of the pits is found to be the supersaturation of
iron carbonate where the iron ion and carbonate ion concentration affect the solubility
of the iron carbonate product [50]. The kinetics of iron carbonate film is another
important factor to maintain the favourable conditions [25]. Pitting propagation could
possibly take place when moderately protective iron carbonate forms, which is
typically at a temperature between 50°C and 90°C, and pH 5.5 to pH 6.6, as shown in
Figure 3-7 [25, 50, 87, 88]. A higher chloride concentration increases the solubility of
the iron carbonate film making it more difficult to form a protective iron carbonate
and more likely to result in pitting propagation [50, 15,28,88].
SSFo<rF~ = 0.5 2
-..
20
\ Gra
E 18
\
a.
a. 16 \ FeCO] precipitation area
'\
'-"
c \ Low uniform corrosion rates
14
-co
.2
-~
c
a.>
0
c
12
10
8
_
\
\
~ \
~~~e.:'..a~~~t:~ ~~I~-"__ ~ _ ~~ ___~~:~.?~u~~t~ ~~~~ _________ ~
\
0
<-)
it
6
4
\
Bare steel corrosion area "
" '
.....
a.>
LL
2
0
High uniform corrosion rate
5.2 5.4 5.6

.........
5,8
--
6 6.2
--
6.4 6.6 6.8 7
5
pH
Figure 3-7: Calculated pH effect on solubility of FeC0 3 and the grey zone at T=80°C,
PC02=0.53bar, 1% NaCI [50]
32
Pit propagation is not a continuous process and may stop if the protecti ve iron
carbonate film starts to re-form on the surface, however, if the solution conditions
remain favourable, rapid pit propagation may continue until the point of line failure
[15, 50]. Pitting corrosion can best be explained by establishing the relationship
between the corrosion rate and the depth of the pit [22, 89].The absolute maximum pit
depth was found to be a function of both the period of exposure and area of exposure
[70].
3.4 Sweet corrosion inhibitors

Corrosion inhibitors are widely used in the oil and gas industry to protect the
pipelines in sweet and sour environments [6, 16, 27, 90]. Sweet corrosion inhibitors
are often a blend of an actively adsorbing chemical typically consisting of amines,
imides, imidazolines, salt of nitrogenenous molecules, nitrogen quaternaries and many
others depending on the application [47, 48, 91, 92]. Corrosion inhibitors are
influenced by its pH buffering ability, surface activity and film forming barrier
properties [60, 79]. Corrosion inhibitors mainly comprise two processes that start
with adsorption of the inhibitor leading to inhibition of the anodic reaction and the
second process, which leads to a reduction in the corrosion rate through inhibition of
the cathodic reaction [3, 91, 93-95].
The inhibitor molecule structure actually changes the electrochemical reaction

rates by influencing the mass transfer of reactants or reaction products or simply
blocks parts of the active surface area [91, 95]. The more the inhibitor molecules are
adsorbed and cover the surface of the metal, the more the active corrosion site is
blocked and the remaining corrosion reaction that occurs is from areas that are
inhibitor free [93,95-97].
The synergy between the iron carbonate and inhibitor offer corrosion
protection. Depending on the type of sweet inhibitor, the iron carbonate may change
the crystalline morphology of the film to become more protective [98-100]. Some
inhibitors hamper the growth of iron carbonate and some inhibitors stop the growth of
iron carbonate [98-100]. Sweet corrosion inhibitors are also capable of preventing
underscale corrosion and pitting corrosion if suitable doses are applied [9, 60, 10 1].
33
High performance inhibitors usually lower the general corrosion rate to 0.1 mmlyr
without incurring any pitting attack [6, 102, 103]. However, most localised corrosion
inhibitors provide protection in terms of pitting attack but usually reduce the amount
of general corrosion [102, 103].
3.4.1 Imidazoline inhibitor

Imidazoline is a nitrogen based organic surfactant that is commonly used to
protect mild steel in oil and gas wells and pipelines from carbon dioxide and hydrogen
sulphide corrosion [104]. The generalised structure of irnidazoline is shown in Figure
3-8. Imidazoline is typically prepared from a long chain fatty acid and a polyamine
that is dissolved in an aromatic solvent and dispersed with glycolic acid and he xylene
glycol [91, 92]. Depending on the concentration, imidazoline is fairly soluble in CO 2
containing brine and influences the bonding of molecules with iron [90,91,104]. The
surfactant molecules in the solution will form an adsorbed surfactant monolayer or
bilayer on the metal surface [105]. The inhibitor film formation could be explained
by the increase in bilayer cohesive energy with the hydrocarbon chain to provide a
barrier to water and chloride ingress [98, 105]. Imidazoline inhibitor is also found to
interact with Fe 2+ creating a Fe complex and decreases the corrosion rate by
preventing the growth of iron carbonate [98].
Figure 3-8: Generalised structure of saturated straight chain imidazolines [98]
3.4.2 Phosphate ester inhibitor

Phosphate ester type inhibitors are a reaction product of ethoxylated,
propoxylated or butoxylateda1chohols or phenols with a phosphating agent [92].
Phosphate esters are green corrosion inhibitors and are biodegradable and safe for
organisms that inhabit the general corrosion in oil and gas wells and pipelines [92.
106]. The generalised structure of phosphate ester is shown in Figure 3-9. The
34
reaction of phosphate esters with nitrogen base inhibitors could provide suitable
inhibition for localised corrosion [92, 106]. Phosphate esters are used to complex with
F 2+ d F 3+ . .
e an e to form Insoluble Hon phosphate, which prevents further corrosion
attack [98, 106]. Phosphate ester efficiency is closely related to its minimum effective
concentration, which plays an important role in stabilising phosphate esters against
2
Fe + catalysed hydrolysis [106].
Figure 3-9: Generalised structure of phosphate esters [98]
3.5 Sour corrosion in carbon steel

Sour environments are characterised by the presence of both hydrogen
sulphide and carbon dioxide in the system [68,107]. Hydrogen sulphide and carbon
dioxide gas dissolve in the water turning the water acidic and corroding the steel
surface [108, 109]. Sour corrosion is influenced by various operating parameters such
as H 2S/C0 2 gas composition, temperature, pH and water chemistry [8, 110]. The
reaction of H 2S and the steel may form an iron sulphide film on the steel surface and
function as a barrier to protect the steel by reduce the corrosion rate [110]. Hydrogen
sulphide tends to accelerate the corrosion rate in the initial stage until a protective film
forms on the metal surface [1, 111, 112].
There are many types of iron sulphide film and, commonly, the protective
iron sulphide film is composed of a mixture of iron sulphide (mackinawite) FeSl_x and
iron carbonate (siderite) FeC0 3 [51, 24, 113]. Iron sulphide films predominate in sour
environments in which the sulphide concentration plays an important role in
determining the film characteristics [41,111]. Iron carbonate is a secondary product in
sour environments, and typically, it offers less protection compared with iron sulphide
films [79]. Hydrogen sulphide is three times more soluble in water compared to
35
carbon dioxide but is a weaker acid in water compared to carbon dioxide [5, 2'+]. Sour
corrosion just needs the H 2S/C0 2 ratio to exceed 1/5000 to form an iron sulphide film
[5].
3.5.1 Electrochemistry of sour corrosion

Hydrogen sulphide will dissolve in water and take part in a cathodic reaction
[51]. Hydrogen sulphide corrosion will form an iron sulphide film on the metal
surface; the corrosion mechanism is described as follows: [1,24,51,108,111,11'+,
115].
The anodic dissolution for the iron in aqueous solution is as follows:
Anodic reaction:
Iron oxidation
Fe(s) ---+ Fe+ 2(aq) + 2e- 3-10
The cathodic reaction is the reduction of hydrogen ions derived from H 2 S to H2 [1]
Cathodic reaction:
Hydrogen sulphide dissolution:
H2S(g) ~ H2S(aq) 3-11
H2S(aq) ~ H+(aq) + HS-(aq) 3-12
Bisulphide dissolution
HS-(aq) ~ H +(aq) + S'-

- (aq) 3-13
Hydrogen sulphide reduction
3-14
Bicarbonate reduction
3-15
36
Formation of the iron sulphide takes place

By precipitation
3-16
By direct solid state reaction:
3-17
An iron sulphide film will form very quickly to cover the surface with a black
film of sulphides [51, 108, 114, 115]. Hydrogen sulphide corrosion is divided in two
stages [1, 111, 112]. In the first stage, the corrosion rate will accelerate; the process is
primarily by the diffusion of ferrous iron through the iron sulphide until the plateau is
reached [1, 114, 116]. Another pathway for iron sulphide formation is by the direct
reaction from H 2 S with fast oxidation of solid iron, which transforms directly into
solid iron sulphide attached to the steel surface [24, 116]. The corrosion rate will start
to decrease when the protective corrosion film is formed [114]. The metal loss due to
diffusion controls the growth of the iron sulphide scale for 20 hours, after which the
corrosion rate become constant controlled by the dissolution of scale into the aqueous
environment [116].
3.5.2 Influence of operating conditions

The protective film in sour corrosion mainly depends on the factor of H 2S
concentration, H 2S/C0 2 partial pressure, temperature, pH, chloride concentration and
immersion time [4, 11, 107, 115, 117]. Supersaturation and temperature are important
parameters that affect the film accumulation rate to define film morphology and film
protectiveness [4, 118].
3.5.2.1 H2S concentration

H 2S concentration plays an important role in determining the characteristics of
the sulphide film and pitting ability on carbon steel [Ill, 117, 119]. A high
concentration of hydrogen sulphide can slightly accelerate the corrosion rate
depending on the protectiveness and characteristics of the iron sulphide scale [1101.
37
However, at lower H2S concentrations, the corrosion rate would decrease significantly
[110]. CO 2 concentration does not have a significant effect on the corrosion rate under
°
H 2S dominated conditions [110]. A concentration of 1 ppm of hydrogen sulphide in
the solution will lead to a rapid and significant reduction of carbonate film rate [68,
118]. Hydrogen sulphide corrosion starts to accelerate the corrosion rate at H2S
concentration of 25ppm [68, 118].
3.5.2.2 Temperature
Temperature is not sensitive at lower H 2S concentrations; increasing the
temperature will increase the corrosion rate for a period of time and then become
constant [110]. At higher H2S concentrations the temperature may change the type of
FeS and the protectiveness of the film, which affects the corrosion rate [110, 120,
121]. Temperature influences the thermodynamic process related to the film
compositional and morphology, which forms a more protective and stable Iron
sulphide film compared to the film at lower temperature [110, 120, 121]. Increasing
the temperature also increases the solubility of FeS and decreases the solubility of
FeC0 3 [122].
3.5.2.3 Solution composition

Solution composition factors are important parameters that have an effect on
sour corrosion, such as pH, Fe 2 + concentration, chloride concentration, organic acid
and brine composition [110]. The overall corrosion rate is found to increase with a
decrease in pH at lower H 2S concentrations. This is because the solution is
undersaturated with respect to sulphide ions, which cause the FeS film to dissolve [1,
68, Ill, 115, 117]. When the pH is kept constant, even in high H~S concentrations,
the solution may become supersaturated and form a stable iron sulphide film [110].
The Fe 2+ concentration has a negligible effect on the H 2S corrosion, as the FeS scale
is relatively small and easy to reach supersaturation level [110]. However, Fe 2+ may
affect the sour corrosion at lower H2S concentrations [110]. The chloride
concentration will affect the corrosion rate as a more permeable sulphide scale forms
on the surface at higher chloride concentrations [12]. Higher chloride concentrations
might also impair the iron sulphide film consistently and lead to pitting attack [110].
--t-Ih Ili~IVERSnY :!8Ri-IRY

38
3.6 Sour corrosion films

In sour corrosion of mild steel, both iron sulphide and iron carbonate layers
can form on the surface [123]. Iron sulphide films comprise mainly iron sulphide
amorphous ferrous sulphide, mackinawite, cubic ferrous sulphide, smythite, greigite,
pyrrhotite, trollite, kansite, marcasite and pyrite [1, 4, 110, 114-116]. The type of iron
sulphide film that will form depends on the thermodynamic and kinetic process of the
growth. The thermodynamics will determine the stability of the FeS species in a given
environment and the kinetics will determine the growth rate of the film [109, 110].
The domains of stability of various iron sulphide species in the temperature and
composition diagram are shown in Figure 3-10 [124].
I ttoilite plus low temp. I I

150 I I iron hexagonal I I
1.1 oyrrhotite I I
monoclinic pyrrhotite I I
I-~.,. ..... - - -
I I I I plus pyrite I I
I I I I I I
I I I I I I
100
I I
I I
I I
I I
I I
I I 3:
-Q)
:';:;0)
0_
..c. :;::;
L.. 0
I I
I
I ;
I
pynte piUS
monoclinic sulohur
I I I I ..Q L...r::. I
1:51 ~ - >-L..
o.L.. I I
Temp, I.!:::I
I I
I I g CIl Q)
c _
0:';:;
0.>-
E:;- Fe3S
I I
0>0 Fe7SS I I pyrite
I~I
IJ)
I I _Q) .-c
°C IOj I I
:::J
a. Q)CIlt
- x L.. I I
;':Q)>- 3:'8 monoclinic I I
I~I I~I ~ o .r::. 0. o
- c
0 pyrite plus
I~I I~I ;: ..b w
0.
. - 0 pyrrhotite Re 3S4 Orthorhombic
50 :::J
~ E plut p~rite
til
I~I I~I c -o.Q)
E plus Fe3S4
101 101 :g ~ ..... o If) sulphur
I til
EI
til
lEI
til
O>:::J
CIl_ I I
E 0
x 0.
Q) I I
I I I I ~ .r::.
I I I I I I
I I I I I I
I I I I I I
J .J I I I
100 52 51 50 49 48 47 46 45 44 43 42 34 33 32 31 30
ATOMIC PERCENT IRON

Figure 3-10: Temperature-composition diagram for the iron sulphide system [124]
A thin FeS film is often formed in a short duration of time and with an
increased exposure time, a heavier film will form with more complicated layer
structures and more than one type of FeS [110]. Figure 3-11 and Figure 3-12 shows
the surface morphology with time [5].
39
Figure 3-11: SEM image of FeS after 3 hours exposed time at 50% H 2S, 50% CO 2,
60°C, pH 5 [5]
Figure 3-12 : SEM image of FeS after 24 hours exposed time at 50% H 2S, 50% CO 2 .
Small amounts of H 2S lead to a rapid and signific ant reducti on of CO 2

corros ion rate. whic h is associated with the formation of iron sulphide on the sUlface
40
[24]. There are three different regImes In the C0 2/H 2S systems that are cI a sified
based on the concentration of H 2S, as shown in Figure 3-13 .
:. ": ~ :~ . : ::: :.:.::.

• H2 S regi~e •.•.
CO 2 regime
sweet
Figure 3-13: COlTosion regimes in C02/H 2S corrosion [24]
Non-protective film s in sulphide mainly compn se loose and blittle

mackinawite coarse grains, which lead to film fracture and adherent mackinawite
tends to support pit growth and localized attack [24, 114] . The formation of iron
carbide in sulphide films also promotes the formation of non-protecti ve films , whi ch
tends to accelerate the corrosion rate [54]. An iron sulphide film will form as a
metastable species mackinawite and will transform due to salinity change to a more
stable species trolite, pyrite and pyrrhotite [8 , 12 , 115] . The transformati on may
change the behaviour and protectiveness of the film [8, 114] . If the transform a ti on is
due to an increase in salinity, a heavier and more permeab le sulphide film will form ,
which often leads to pitting under the scale [12]. The relationship between the type of
corrosion product that forms as a function of temperature and H 2S concentration is
shown in Figure 3-14 [24, 113] . The boundary of mackinawite region and pyrrhotite
region is defined by the solubility of FeS in the bulk so luti on [113]. When the FeS is
below the saturation limit in the bulk fluid and H 2S is greater than the leve l required
then the mackinawite is the cOlTosion product [113]. When the FeS le vel s in the bulk
fluid mee t or exceed the saturati on leve ls, the reaction kinetic finall y all ows PYIThotite
to become the cOlTosion product [113] . Iron sulphide film s pro vide better conducti vity
41
compared to iron carbonate films [8, 61, 124]. In the cathodic reaction for carbonate
film, the process of transporting the reaction, protons and carbonic acids will
penetrate under the film or at the defect to reach the metal surface [8]. However, for
sulphide films, the cathodic process can occur on the film without being restricted by
diffusion through the film [8]. Localised attack will start to take place if the local
supply of H 2 S is not sufficient to reform the sulphide film [8].
Oilfield Corrosion Products
Cubic FeS
Q)
~
::J
C5
~ Pyrrhotite
Q)
0..
E
Q) Mackinawite
I-
log H2 S Activity
Figure 3-14: Corrosion product relationship [113]
3.6.1 Mackinawite
Mackinawite is a metastable form of FeS that forms in the presence of small
amounts of H 2S [24]. Mackinawite is usually the dominant iron sulphur product and
forms first then transforms into greigite or pyrrhotite and finally pyrite, as shown in
Figure 3-15 [109, 120, 124]. The formation of mackinawite is very rapid and the
composition contains between 50.9 to 51.6 atomic percent Fe [109]. Mackinawite is
the predominant species at low H 2S concentrations and when the concentration
increases, mackinawite might be substituted by pyrrhotite and then pyrite [125].
42
PYRITE MARCASITE
FeS2 FeS 2
Cubic Ortho-
rhombic
Jr
IRON
Fe 2+ "" .. MACKINAWITE
FeS,_x
GREIGITE
Fe 3S4
Aqueous
Tetragonal Cubic
J[ j
SIDERITE
SMYTHITE
FeC0 3 PYRRHOTITE
Rhombo-
hedral
.. Fe3S4
Rhombo-
Fe,_xS
Ni As type
hedral
Figure 3-15: Summary of the major Iron sulphur inter relationships In aqueous
solution [124]
3.6.2 Pyrite
Pyrite formation from the mackinawite and greigite reaction with vanous
sulphur species involves a complex multi step reaction mechanism to convert FeS to
pyrite [109]. The rate of conversion is very slow in comparison to mackinawite
formation and the kinetics of the formation reaction is shown in equation 3-18 [109].
Pyrite formation is associated with high H2S partial pressure and believed to require
elemental sulphur [24].
FeS + S ~ FeS2 3-18
3.6.3 Pyrrhotite
Pyrrhotite is a non stoichiometric of FeS that forms hexagonal close packed
(Hep) crystals [109]. Pyrrhotite is believed to be more thermodynamically stable than
mackinawite because the pyrrhotite formation kinetic is much slower than
mackinawite [24]. Pyrrhotite generally contained 46.5 to 48 per cent Fe in the study
sample [109].
43
3.6.4 Amorphous FeS and cubic FeS

Amorphous iron sulphide is limited as it is unstable and either dissolves or
transforms into mackinawite very quickly [109]. Cubic FeS seemed to form in the
neutral pH range and was also found to gradually transform to mackinawite at room
temperature [109]. Cubic FeS did not form in the presence of oxygen and chloride
[109].
3.6.5 Smythite and greigite

Smythite deposits tend to form in hexagonal flakes much like pyrrhotite and is
strongly ferromagnetic. It has a similar overall crystal structure to pyrrhotite along the
axis but is stacked differently [109]. Greigite is a polymorph of smythite with a
nominal composition of Fe2S4 [109]. Greigite is often an intermediary between
mackinawite and pyrite and the oxidation of Fe 2+ and Fe 3+ may play a role in the
transformation [109].
3.7 Sour pitting corrosion on carbon steel

The majority of corrosion failures that occur in sour oil and gas production,
down hole tubing, pipelines and equipment constructed from carbon steel are
attributed to localised corrosion [126]. The presence of sour gas invariably causes
localised corrosion if the produced fluid is not treated properly and will quickly result
in failure [126]. A sensible approach towards predicting and mitigating localised
corrosion is through improving the understanding of the behaviour of iron sulphide,
especially the interaction between protective films and pits [127]. The iron sulphide
scale that forms on the steel surface can be very protective but localised corrosion
attack may occur in the presence of high chloride levels, elemental sulphur or
exposure to stagnant water [12S]. The higher corrosion potential difference between
sour scale and steel causes greater pitting tendency in sour corrosion compared to
sweet corrosion [72]. The precipitated film forms on top of the existing mackinawite
films, decreases the effect of flow, and increases the overall corrosion rate and
probability of localised corrosion [114, liS]. Figure 3-16 shows the SEM image of
pitting growth under the sour film [liS].
44
&p I MP
65 1 ~ 1 2.) d3)'
Figure 3-1 6: SEM cross-section image showing pit growth under film on X65 carbon
steel at T=60°C, pH=6, PC02=0 .77Mpa, H 2S at 25ppm , and V= 1m/s for 30 days
[ 118]
There are several methods to characterise pitting COITOSlOn , such as pit

initiation, pit propagation, repassivation, total number of pits, average pits and
maximum pit depth [21 , 129] . Sun et al. characterised pitting corrosion by pit
initiation, pit propagation and repassivation [129]. Propagation of pits is a kinetic
process and wi ll normally lead to the failure of the facilities [129] . Stewart et al.
characterised and ranked the maximum pit depth because it represents the worst case
scenario that leads to fai lure, as shown in Figure 3-1 7 [21].
Blank A B c D
§....... 60
6
'-' •
.£:
4
+-'
Q.
.
(l)
0 19 1
.-t= 40 2
0..
E
::J
2 • ·
6
.
2
E 4 • •
4 3
x
ro 4
I • •
~ 20 • •
5 1
• • •• • • 2
•
• 2
2 • • I • I
• 1 1
• I • • I2 • • o
o 0 000 0
0
Rl R 2 R 3 R4 R5R6 R1R 2 R3R4R5R6 R 1 R~R3P4R5R6 R1R2R3R4 R5R6 R 1 R 2R3R4R5
Run #
Figure 3- 17 : Pit depth measurements and pit counts for blank te sts and inhibitors [21]
45
3.7.1 Sour pitting corrosion process

Iron sulphide films on the carbon steel surface can be very protective but
depending on the various environmental factors, the different thermodynamics in
some cases can be non-protective and results in localised corrosion [2-+. 128, 130].
The changing form of the iron sulphide layer can develop internal stress in the film
and can lead to film fracture that causes the potential of localised attack [2-+. 128,
130]. The change in the electrochemical kinetics will also increase the corrosion
potential over time and lead to a region where local breakdown of the protective film
and pitting corrosion could occur [119, 124, 128, 131]. This will lead to the situation
where the area at the film breakdown becomes small local anodes and the film area at
the steel surface will work as efficient cathodes [114, 124]. The corrosion product
films consist of iron sulphides, mostly mackinawite, and are more porous and
apparently less protective [131,132].
3.7.2 Sour pitting corrosion initiation

There are various ways how pits are initiated in a sour environment. Steel
microstructure, such as manganese, sulphide inclusions plays an important role in the
pitting initiation in X65 carbon steel due to SUlphide inclusion and mixed manganese
and iron sulphide films [124]. These promote pitting attack by acting as weak points
in the metal surface and have been found to act as susceptible spots for the nucleation
of pits [124]. Another way of pitting initiation is due to the Fe3C phase that is left
behind, the cathodic reaction is supported by the iron sulphide film and the anodic
dissolution of ferritic iron will proceed beneath the films. This may result in
undermining of the film and the Fe3C phase with subsequent groove formation, which
may eventually grow into pits that consume the ferrite grains surrounding the pearlite
[130].
The other way of pitting initiation is if the metal surface is not fully covered
with iron sulphide or if the film breaks down in certain locations [126]. This will
create an anodic site on the metal surface and the iron sulphide area will act as
cathodic sites [126]. Consequently, there will be a situation of a small anodes and a
large cathode set up on the metal that will accelerate corrosion at the anodic sites that
will cause pits to form [126]. Kvarekvnal found that pits in sour environments can be
46
of many different shapes and types under identical cond iti ons [130] . M oloney et a!.
found that many smaller pits are initi ated adjacent to eac h other and initiate near the
larger pits [133].
3.7.3 Sour pitting corrosion propagation

Under some conditions a transient pitting mechanism can take place in whi ch
pits are initiated for a limited period of time [1 32]. Pit depth does not vary
significantly with the exposure time, which indicates that the process of pit initiati on,
growth and passivation takes place within a rather limited space of time [ 132] . Pit
growth is decelerated or maybe even stops after a w hile, probably due to the
accumulation of corrosion products in the pits [132]. The incubation time between pit
initiation and the maximum pit depth appears to be independent of the duration of
exposure time [132] . The pit growth rate may decrease with time and the n stop
growing in some cases probably becau se of the deposits of solid con-osion products in
the pits [132]. Kavarek val et a!. shows a cross section im age of 50~m pit
accumulation of con-osion products as shown in Figure 3- 18 [132].
Figure 3-18: SEM picture of a pit filled with con-osion product [132] .
Sun et a1. indic ated that the pit propagation rate under a sour environment is a
nonlinear process with respec t to time due to passivati on and repassivati on takin g
place to reduce the pit propagation rate [1 29]. In addition , Stewart et a!. shows th at pit
depth inc rea ses over time, which mean s that longer tes ts will generate more se e re
loca li sed corros ion and thu s deeper pits [1 34]. Stewart et a!. obse rved that larger pit
47
were severe enough to last for most of the 72 hours test durati on [134] . Mo loney et al.
indicated that the speed of pitting rate is due to localised high Fe 2+ concentrati on from
pitting leading to saturation of salts, such as iron chloride (FeCh), iron sulphide (FeS),
iron carbonate (FeC0 3) within the pit mouth [133] . These will impede the irons
travelling to and from the active pit metal surface retarding the pit from propagating
further and resulting in consequential pit death [133].
3.8 Sour corrosion inhibitors

Corrosion inhibitors are typically applied in oil and gas production to mitigate
corrosion caused by the presence of sour gases [18 , 123] . Most laboratory testing
methods are only suitable to assess inhibitor performance in preventing general or
uniform corrosion [126] . Additional corrosion monitoring techniques should be used
to confirm that pitting corrosion is not taking place and optimise the inhibitor
concentration accordingly [126]. The ability of the corrosion inhibitor to interact with
those layers determines the effectiveness of the inhibitor and its ability to prevent
pitting [135]. The performance of the inhibitor is determined not only by the
absorption of the steel sUlface but by its ability to bind into a product layer providing
protection and changing the morphology of future scale growth , as shown in Figure 3-
19 and Figure 3-20 [135].
Figure 3-19 : SEM image after 14 Days at 3% NaCl , pH 6, 689Kpa H 2S [1 35] .

48
Figure 3-20: SEM Image after 14 Days at 3% NaCl, pH 6, 689Kpa H 2S with
inhibitor[ 135].
Moloney et al. showed that corrOSIOn inhibitors that provide hi gh general

corrosion inhibition may not always offer locali sed corrosion protecti on [7 , 27 ].
Furthermore, Jenkin s determined that hi gher dose rates of inhibitor are required to
prevent locali sed corrosion compared to the dose rate required to prevent ge nera l
corrosion [27 , 126]. Schmitt et al. showed that adding inhibitors at sufficient
concentration on pre-corroded specimens may stop pitting corrosion [27] .
The inhibition effect is related to the formation of a protecti ve layer with

ferrous sulphide grains on the electrode surface [lIS]. The metal surface is practically
always covered with a protective film and the build up of adsorbed inhibitor results in
a synergetic effect in the common protective activity [18] . Sastri et al. showed that the
inhibitor layer was detected using XPS at the outer laye r of the film to prevent the
di ssolution and recrystallisation of the lower iron sulphide layer [136]. The type of
inhibitor is important so that the most appropriate chemical is se lected to contro l the
corrosion process [1 2]. There are many types of sour corrosion inhibitor; one of the
most com monl y used is a cati onic inhibitor composed of cyclic aliphatic and aromatic
amine complexes with non -i onic surfac tants [12]
49
Stewart et al. evaluated sour inhibitors in terms of the maximum and average
pit depth penetration and analysed the depth/size and distribution of the pits in
conjunction with the electrochemical technique [134]. Moloney et al. described that
some inhibitor tests that resulted in deeper pits than were observed on the blank test
could be the adverse effect of the corrosion inhibitor interaction with various
chemistries contained in the test environment, and which could result in nullification
of the corrosion inhibitor or may be based on the competitive adsorption of the
molecules within each product of the metal surface [7].
3.8.1 Type of sour corrosion inhibition

Inhibitors have often been used to control sour corrosion such as substituted
imidazolines, alkyl pyridine quartenary amines, phosphate, nitrates and substitutes
amines [116,136, 137]. Inhibitors may assist in generating a protective layer by
forming a thin and effective barrier layer on the metal surface that will resist the
chemical attack of liquids and gases [136]. This will also reduce the dissolution of
scale into the aqueous environment and it may also hinder the diffusion control led
growth of iron sulphide scale or prevent spilling of the scale surface [116, 136].
Schmitt et al. showed that inhibitors affect the morphology of iron sulphide by
making the scale thin, smooth and adherent to the surface compared to without
inhibitors in which it is thick, rough, and spongy with a poor adherence scale [138]. It
was also found that the best performance inhibitors have the smallest scale thickness
and provide good protectively [138]. Schmitt et al. found that amide derivatives with
alky group inhibitors provide a good general corrosion and localised corrosion
inhibitor [138]. Park et al. showed that corrosion inhibitor appears to change the
crystal morphology [135].
Imidazoles have two types of nitrogen type inhibiting forms - pyridine and
pyrrole. These are considered to influence the bonding of molecules with iron, as
shown in Figure 3-21 [104]. Pyridine and substituted pyridine compounds have been
used as inhibitors in a medium consisting of sodium chloride solution in sour
environments [137]. Bhargava et al. showed that imidazole can react with metal if it is
able to reach Fe through the channels formed in the oxide layer, which provides a
greater surface coverage and protection [104].
50
Pyridine
type N
.. /
0 N
() N..........
I I Pyrrole
H H type N
(a) (b) (C)
Figure 3-21: Molecular structure of a) pyridine, b) pyrrole, and c) imidazole
Amines and quaternary ammes are popular inhibitors for use in sour gas
applications [21]. Stewart et al. reported that amine based inhibitors exhibit good
ability to inhibit pitting corrosion in a range of brine conditions and highly sour
environments [21].
Field trials show that the amine based inhibitors slightly decrease the iron
concentration and general corrosion rate as well as pitting corrosion in the system
[21]. Wang et al. showed that many of the shallow pits observed after removing the
black surface scale and the pitting were further prevented by the presence of the
inhibitor [139]. A mixture of imidazoline and coco benzyl quaternary ammonium
inhibitor could greatly reduce the general corrosion and significantly reduce the
localised attack [139].
3.9 Environmentally friendly corrosion inhibitors

Corrosion inhibitors continue to play an important role in controlling internal
corrosion and research efforts are necessary to develop corrosion inhibitor products
that are more acceptable to the environment than the conventional types of inhibitor
[138]. In recent years concern has increased concerning the environmental impact of
the chemicals being used leaking into the environment and the toxic effect on the
marine life [138]. Inorganic inhibitors were first developed by the use of inorganic
salts or blends including chromates, nitrites, phosphates, borates, silicates, zinc salts
and other cations [31,40]. The use of anodic inhibitors such as nitrites and chromates
51
requires a high initial dose in order to achieve an effective passive layer on the metal
surface; however, the concentration can be reduced in the presence of polyphosphates
and zinc ions [31]. Zinc ions inhibit by the cathodic polarization mechanism and in
combination with phosphates will lead to a protective film. The protective films
caused by cathodic inhibitors are macroscopic and are mostly easily visible, whereas
anodic inhibitors will generally form very thin, hardly detectable passive films.
Although inorganic inhibitors provide reliable corrosion protection in aqueous
solutions, the discharge or inorganic material has become increasingly unacceptable
[30, 31, 40]. Organic inhibitors have been used to reduce the chemical impact on the
environment and ensure chemical degradability under mild conditions and
biodegradability. The most commonly used organic inhibitors are orthophonates,
pyrophosphate, gluconates, phosphonates, polyacrylates, soluble oils and carboxylates
[30,40].
3.9.1 Corrosion inhibitor legislation

An improved understanding of corrosion inhibitors has led to a more
environmentally acceptable chemistry that meets and exceeds the regulatory
requirements. The legislative bodies have drawn up a set of guidelines on
environmentally friendly or green inhibitors [39]. The regulations require chemicals
for field applications to have specific properties regarding biodegradation, toxicity
and bioaccumulation according to OSPAR guidelines (Convention for Protection of
the Marine Environment of the North-East Atlantic) [39, 140].
The Norwegian authorities have divided offshore chemicals into four colour
categories - black, red, yellow and green. The worst-case chemicals, categorised as
black, are not permitted to be discharged unless in exceptional circumstances. Red
category chemicals are to be phased out and banned. Yellow category chemicals are
permitted and green chemicals are those listed in the PLONOR. The yellow category
requirements include the following [39]:
• Biodegradation> 20%
• Log Pow < 3
• Toxicity> 10mg/1
52
For Norway, test data are required on biodegradation, bioaccumulation and toxicity
according to OSPAR guidelines.
The UK legislation accepts extended marine biodegradation data beyond 28

days and also fresh water biodegradation data. Once the ecotoxicological data have
been generated, the results are then entered into the pre-scheme. Typically, if the
biodegradation of a chemical is more the 20% in 28 days then it is then judged
according to the following three criteria [39]:
• Biodegradation < 70% (OECD 301A, 301E) or < 60% (OECD 301B,
301C, 301F, 306)
• Bioaccumulation log Pow> = 3 or BCF > 100 (considering molecular

weight)
• Toxicity LC50 or EC50 < 10mg/1
If it then meets two out of three criteria, it is placed on the substitution list and is
flagged for substitution [39].
3.10 Artificial pitting experiments

The artificial pit experiment setup was developed for inhibitor development
testing to address the ability of the inhibitor to affect localised corrosion that is
already propagated at a known rate [50, 69, 141]. There are various types of artificial
pit techniques that have been used to accelerate the pitting process - pencil artificial
pit, artificial pit, mechanical punched, drilled, electrochemical and chemical [69].
Turnbull et al. used the pencil artificial pit technique to generate the same pits
repetitively in a controlled manner in both sweet and sour environments [69, 142-
144]. The anode is formed by mounting a steel rod of small diameter in epoxy and
pre-corroding it to a specific depth and coupled via a zero resistance ammeter (ZRA)
as shown in Figure 3-22 [69]. This technique is flexible since the amount of pre-
corrosion and pit depth can quite easily be altered and it is able to evaluate inhibitor
performance [69, 143, 144].
53
LJoLble IU -ctJ::a
I<&rerence eloclIo:le rt-fe-eflce. f:o - cu od!
--. . . .
J
,
-.----_. E CGb1C,JI \.,, .
~o ~ n€t ~ U O [\
". '; - : Lug; " : U~EI
.--I....l \ - - : +---
J
~I
-
- - - - _ . ",0
- - . --::-~ . . . . --
::
::
Flim~i l +IrtifioOJI
.~~~-- ~-=--= =-~ ~

~H ae ~lImc l 'p'
- - . ., =.
RatJ lintl LJ 1ince,
el~r o~e
AgzII gd
s<l ll bn:;\:.)c
Figure 3-22: Schematic of two-compartment cell for pencil artifici al pit experiment
[69] .
Marsh et al. designed an artificial pit-bar test consisting of zero resistance

ammetry (ZRA) measuring the current between an artifici al pit electrode connected to
a counter of the same material but of much larger area [141] . The wire electrodes
were recessed by anodic pol arisation in an ac id solution to ac hieve the required pit
depth [141]. The inhibitor performance was tested in sweet and sour environments
with respect to inhibition of general corrosion and locali sed corrosion [141] .
Han et al. coupled a bare steel surface that acted as an anode and FeC0 3 layer
covered steel that acted as a cathode in a conductive CO 2 solution . Nesic et al. used
the mechanical and chemical film damaged technique to study film breakdown and
pitting [26, 42, 43] . The mechanical film damage technique used hydrodynam ic force
to partially remove the film , whereas the chemical film damage technique used
di ssolution removal by mass tran sfer control to parti ally remove selective film that
exposed an area of open pores on the film , as shown in Figure 3-23 [42, 43] . The
difference between these techniques is in the kinetic s of the process; it appears that
the film di ssolution produces a better effect compared to mechanical film remova l
[26].
54
Figure 3-23: Typical surface topography of FeC0 3 film at the e nd of di sso luti o n
process at 10000rpm velocity , pH 5 .8 [43] .
3.11 .nt-situ pitting experiments

Direct observation of the characteristics of pitting form ati on requires too ls
with the appropriate reso lution and that are suitabl e for in-situ stud y. The tec hnique
should be able to observe the initiation and growth of pits and assess the inhibitor
activity toward s pitting on carbon steel surfaces in sweet and sour conditi ons. Of the
many techniques that have been used , one of the most appropri ate is by Dave nport
using in-situ synchrotron X-ray diffraction . Thi s technique can obtain the inform ati on
on crystallite size , which influence s the tran sport properties of the film and the
roughness of the underl ying metal [67] . In- situ X-ray absorpti on spectro scopy and
electrochemical impedance spectro scopy can also be used to obta in quantitati ve data
during a lloy pass ivation [74, 76].
The in- situ imaging technique using optical video and camera in conjuncti on
with electrochemical measurement was used to m onitor crystalli sati on of calci um
carbonate and pitting on stainless steel [78 , 145 ]. Thi s tec hnique can map and monitor
the pits and c rys ta l grow th in real time up to 1flm size [145 , 146 ]. Schm itt et al. used
video mic roscopic control w ith a w indow autoc lave to stud y the parameter of the
pitting initi ati on process under swee t conditions wit hin the observa ti on tim e of 120
minutes [1 46]. These tec hniques indicate that the inhibitor could inhibit pitting
initi ation [146]. Nybo rg improved the in -situ visua li za ti on technique to observe
55
localised corrosion, developed previously by Joosten et aI., to observe mesa attack

growth overtime [47, 86]. This technique has shown that mesa attack in carbon steel
was initiated from several small pits, which grow together in a large mesa attack [47].
There are also techniques that detect the temperature difference during the
pitting process, such as thermal AFM and cyclic thermometry [147, 148]. Thermal
AFM works on the principle of a temperature difference between the localised area to
map the thermal image and cyclic thermometry using a linear thermal program to
measure the critical pitting temperature [147, 148].
Other in-situ techniques can be combined with ex-situ surface analysis

techniques to study pitting, such as the in-situ scanning reference electrode and in-situ
scanning vibrating electrode technique [84, 88, 93, 149-151]. These techniques were
used to map the pitting potential regions and are capable of determining the surface
dimensions of the pits [84, 88, 149-151]. In-situ pitting depth readings can be
obtained using ultrasound sensors as practiced to monitor pitting depth in service
pipelines [152].
3.12 Surface analysis

The nature of sweet and sour films has been extensively studied using
advanced surface sensitive techniques such as scanning electron microscopy (SEM),
electron dispersive X-ray (EOX), Energy-dispersive spectroscopy (EDS), X-ray
photoelectron Spectroscopy (XPS), Atomic Emission Spectroscopy (AES), X-ray
diffraction (XRO) and Secondary ion mass spectrometry (SIMS) [2,48,77, 153-155].
EOX analysis has shown that the distribution of elements through the sweet film cross
section is not homogeneous. The layer near the surface is enriched in carbon and
depleted in iron, however, the layer near the material interface is rich in iron [48]. The
differences in the XPS binding energy between surface and subsurface regions was
attributed to the variation of the chemical environments [2, 156, 157]. The difference
in binding energy for Cis, 0 1s and Fe 2p were found between surface and
subsurface spectra [2]. Applying 30 seconds of argon etching to the surface can
remove carbon and oxygen contamination on the surface [152]. The analysis shows
that the sweet film layers are inhomogeneous and comprise a mixture of iron and
56
complex iron carbonates [2]. Sastri et al. have successfully used XPS to analyse the
inhibitor film and iron sulphide layer under sour conditions as shown in Figure 3-24
[136].
',j_O(A) .1('- Cr(A)

'I
I\. "Cu2p
"\., N2
'-.....' I ' Fe(A)
t~
.~.
\- p
I~Fe(A)
Fe2p Fe2p
/ Ols \.Aj.... 01,
Ni(A) ~/ S2p , Ir 52" Fe3p
,J.,~J.I
l . Mnlp
......,...
~ a(A)NI,
Cls.;,~
\'. ~4
Fe3p
r
l' l I NI- CI.\ ,..~~---'\.l/
Cu(A) .!. I L '""" ·~'·~~U··4 ~
1,000 800 600 400 200 1,OCQ &)0 600 400 2QC o
BE (eV)
Figure 3-24: XPS survey spectra recorded from steel coupons exposed for 96 hours to
deaerated aqueous solution of 5% NaCI CH 3COOH saturated with H2S a) No
inhibitor, b) with inhibitor added [136].
Fourier transform infrared spectroscopy (FTIR) is another surface analysis

technique that is able to obtain information at the molecular level regarding the metal
electrolyte interface [156, 158]. Durnie et al. has used FfIR to identify inhibitors that
are tenaciously adsorbed to the steel [159]. It also provides useful information to
study the mechanism of the inhibitor and evaluates newly developed inhibitors and its
surfactants, such as fatty amido-amines, imidazolines, quaternary amines,
phosphorous and other derivatives [158, 160, 161]. Legrand et al. has characterised
iron carbonate on carbon steel surface and attributed the peaks at 1420, 1345, 1068
and 860 cm- 1 [102, 163-165]. Using this technique, other sweet corrosion products
could be characterised to indicate the corrosion deposit on the surface [165-168].
Various species of iron sulphide have been characterised using FTIR. Romero et al.
1
characterised iron sulphide peak at 1400, 2700 and 2900cm- [169,-171]. Caldeira et
al. and Chernyshova studied the morphology of pyrite and attributed the pyrite peak at
1430 and 1530 cm- l [172, 173]. Baird et al. have studied the mackinawite morphology
and structure using FfIR and identified the mackinawite peak at 310, 435, 674. 1626
and 3384 cm- 1 [156].
57
3.13 Literature review summary

The majority of sweet and sour film surface analysis studies in the literature
have been conducted in environments having a bulk solution pH of greater than pH 5
and temperatures greater then 60°C. Most of these experiments were conducted in the
temperature range of 70°C to 80°C, however, many pipeline operating conditions can
be significantly lower than this.
A mixture of iron carbide and iron carbonate leads to a semi-protective film

that provides little protection to the material. Mixed iron carbideliron carbonate films
are the most common type found on carbon steel under sweet conditions. The films
may change their characteristics to be more protective depending on the build-up of
iron carbonate film over time. The structure of these mixed films also influences their
susceptibility to film breakdown and pit initiation and propagates below the porous
corrosion film by local cell mechanisms.
H2S concentration plays an important role in determining characteristics of the

sulphide film and pitting ability on carbon steel under sour conditions. Hydrogen
sulphide starts accelerating the corrosion rate at H 2 S concentrations of 25ppm where
localised corrosion was observed.
The pitting corrosion process can be divided into a sequence of three steps -
initiation by breakdown of passive film; initiation of metastable pit growth and stable
growth of pits. The chloride ion content is an important factor because it weakens the
protective film and leads to film breakdown and pitting initiation.
The in-situ imaging technique using optical video and camera in conjunction
with electrochemical measurement is a robust technique that can map and monitor the
pits and crystal growth in real time up to 111m size. This technique combines with ex-
situ surface analysis and can be used to study the mechanisms of the action of
commercial inhibitors to improve the inhibitor performance on pitting problems in
sweet and sour conditions.
58
The literature has demonstrated a great deal of research about sweet and sour
corrosion and the interaction of various inhibitors. However, most of the research
concentrates on general corrosion and there are still a number of unknowns about the
corrosion reactions that leads to pitting and the interactions between inhibitors and
pitting. In this thesis, the pitting process will be studied including film formation, film
breakdown, pitting process and its inhibition in sweet and sour conditions.
59
Chapter 4 In-StIli visualisation rig and sour rig design, building and
commissioning and setup
4.0 In-StIli visualisation rig and sour rig design and setup
Thi s chapter is divided into two different te st designs and setups. The first sec ti on
explains the in-situ visualisation design , while the second sec tion explain s the sour ri g
design and procedure for running the rig . The in-situ visuali sati on ri g and sour rig
were developed as part of thi s study project.
4.1 Sweet in-StIli pitting rig

In- situ visualisation using an optical microscope with in- situ electroc hem istry
will be used to study the behaviour of film growth, loc ali sed film breakdown , pitting
growth and assessment of locali sed corrosion inhibitor. The in -situ visuali sa tion rig
for sweet and sour experiments was designed , built and commi ssioned as part of thi s
project study . The imaging method will monitor the interac tion on the sample surface
in real time in conjunction with electrochemical data . The special features of the cell
are the ability to control the temperature up to 80
D
e, indent an artifici al pit and
simulate sweet and sour conditions. Figure 4-1 shows the specimens used and Figure
4-2 shows the sweet in-situ pitting rig .
O-Ring
t
-
10mm
1 0mm
Exposed Area .
1 cm?
Connected to Electrochemis try
Figure 4-1: Specimens for in-situ rig
The rig assemb ly was composed of an electroc hemical ce ll , spec imen ve sel
and ca me ra se t-up . The ca me ra assem bl y contained an adj ustab le le ns to change zoo m
on the objec t, lighting system , camera and image monitor, as shown in Figure 4-3 .
60
The magnification power can monitor the pits initiated on the working electrode as
soon as their size reached illm and followed the growth up to 300llm . B y using im age
anal ysis software, the image obtained over a period of time can be converted into a
short video. Figure 4-4 shows the artifi cial pitting image using different
magnifications.
r------------ ,
I I System
I Camera View I InpuUoutput
I I
I I
I I
I I
I I
I
I
Lighting
I I
I I Input
I I
I I
I I
I
Thermometer
-------------,
Gas Inlet
Camera observation •
Reference!
cyli nder
Working Counter
electrode Electrode
I I
I I
I I
I I
I I
Nylon filter
mesh
Hot Plate
Fiaure
b
4-2: In- situ sweet pitting rig setup
61
Figure 4-3: In-situ pitting rig system
o
Figure 4-4: Artificial pitting image using different magnific ation s
4.2 Sour experiment rig

The sour rig was designed, built and commissioned as part of thi s stud y
proj ec t. The sour experiment simulated the sour environment in an oil field pipe line
w here the saturated hydroge n sulphide and carbon dioxide were pre sent in the
so luti on. The experiment was performed in an enclosed glass cell on X65 carbon stee l
to unde rstand the e lectroche mica l behaviour of the materia l in th e sour so luti on. T he
62
design parameters of the sour cell, as shown in Figure 4-5 , we re si mil ar to the sweet
cell but the emphasis on safety was pri oriti sed due to the ri sk from hydrogen sulphide
gas . Figure 4-6 show s the sour rig . The sour rig contains two experiment ce ll s, whi ch
can perform a single or duplicate experiment at one time. Th e sour rig can also
operate with or without in-situ visualisation equipment.
r ------------"
System
: Camera View InpuUoutput
Lig hting Checking

Input Ive
Gas
Outle t
Camera
observation
cylinder -
Working
electrode
Refere
Counter
Press ure Electrode
Gas Inlet
Relief
Sealing
Va lve
Clamp
Window
sa mple
Hot Plate
Figure 4-5 : In- situ sour ri g test setup

63
Figure 4-6 : Sour rig testing sys tem
4.2.1 Hydrogen sulphide safety

The sour gas system isolated the gas in the system to avoid any escape of the
gas due to the danger of the hydrogen sulphide [174, 175 , 176]. Hydrogen sul phide is
a fl ammable , colourless gas that is to xic at extremely low concentrati ons. It smell s
like rotten eggs at concentrations of less then lOppm and quic kl y causes a loss of
sense of smell w hen the concentration increases [1 74, 175 , 176]. The sour gas
experiment was placed in side the fume cupboard to extrac t any lea k of the hydroge n
sulphide gas. A hydrogen sulphide detec tor was pl aced inside and outside the fume
cupboard to detect any leakage of the gas . Any hydrogen sulphide leakage above
5ppm would make the safety sys tem automatically shu t down the hydrogen ul phide
gas suppl y [174 , 175 , 176]. The risk assess ment and safe ty procedure was fo ll owed
every tim e before starting any sour experiment.
4.2.2 Sour experiment system.

T he sour ex periment syste m setu p is shown in Figure 4-7. The our sys tem
uses a mixture of 10 % hydrogen sul phide (H 2S) and 90 % carbon di oxide (C0 2) as a
sour ga s, and nitrogen (N 2 ) gas as a fl ushi ng gas. A spec ial two-step regul ator is u ed
64
to handle H 2S with N2 as the line flushing gas. The experiment vessel contains 800ml
of test solution with X65 carbon steel submerged inside it. All the glass vessels used
in the sour rig system include a 0.1 bar blow off valve to avoid the glass exploding
due to overpressure. The excess outlet gas flows from the experiment vessel to the air
bottle before entering the H2S scrubbing system to trap any solution passing through
the outlet line. The excess sour gas passes through two sodium hydroxide (NaOH)
traps to pull the H2S gas into the NaOH solution and then oxidises the sulphide to
sulphate. The outlet from the NaOH trap passes through potassium permanganate
( KMn0 4) to oxidise the remaining H 2S before releasing the excess gas to the fume
cupboard extractor [117, 176].
Sour Experiment S~ ,,1 em
()n ()ff Val\~ • IBh'" ()Il \'"h~11 harl
~
Sodium ~
lI~dw,iJc
,:--'"IlII\ I----~
Figure 4-7: Sour experiment system diagram
4.2.3 Operation and emergency procedure of the rigs

The operating and emergency procedure for the sour rig should be understood and
followed by any sour rig operator before running the sour experiment. The full H2 S
system safety protocol was developed as part of the project and details are shown in
Appendix A.
65
4.2.4 Experiment setup procedure

1) Check that all parts of the equipment are safe and ready to use.
2) Test the pipeline (not experiment vessel) at 0.8 bar with N2 and hold the pressure
for 5 minute to check the connection.
3) Increase the test pressure to 1 bar to check the blow off valve is operating.
4) Finish the 1 bar N2 pressure test and release the pressure.
5) Fill the vessel with test solution.
6) Set and activate the temperature control to the experiment temperature.
7) Mount the specimen on the specimen holder.
8) Insert the test electrodes into the vessel and test the electrode assembly.
9) Check the O-ring position.
10) Seal the test vessel.
11) Start the N2 flow test. Test the system with N2 for 15 minutes. (Both inlet and
outlet valves must be open to allow gas to flow through the vessel and scrubber
units.
12) Observe any gas and solution leaking.
13) Observe the pressure indicator to make sure there is no trapped pressure.
14) Finish the N2 flow test.
15) Switch on the H 2S mixed gas and continue purging for the required time. The
person in charge of the experiment must be in the laboratory all the time when
H 2S is in use.
16) Start the electrochemistry test.
17) H 2S gas can only be purged during core hours starting from 0800 until 1700.
18) Following the completion of the gas purging process, close the H2S gas valve.
19) Purge the N2 in the gas line for 10 minutes to clear the gas line from remaining
H 2S gas for 10 minutes.
20) Purge the N2 in the gas line at a slow rate for the experiment that running
overnight to clear any free H 2 S from the test vessel.
4.2.5 Completion of the experiment procedure

1) Switch off the heater and stirrer unit.
2) Allow the vessel to cool to below 50°C.
66
3) Purge the vessel with N2 and the outlet gas should be routed to the scrubber unit
for at least 120 minutes.
4) Slightly open the vent valve on top of the vessel lid.
5) Carefully check the presence of any residual H 2S in the vessel using an alarm. If
any appreciative amount of H2S, more then 5ppm is present, close the valve and
restart purging with nitrogen.
6) Loosen the lid clip.
7) Lift the lid carefully out of the vessel.
8) Remove the specimen from the mounting assembly.
9) Clean the specimen following the experiment cleaning procedure.
10) Empty the vessel. Dispose of the solution into a designated container. (The
solution in the container should be treated by the addition of a H2S scavenger
and mixed with water to remove any H 2S in the solution prior to final disposal).
4.2.6 Helium pressure test procedure

The helium pressure test procedure has been designed to ensure the rig is safe to
use and needs to be undertaken if any modification or change to the sour rig
component has been implemented. The full helium pressure test protocol was
developed as part of the project and details are shown in Appendix B.
4.2.7 Cleaning the scrubber procedure

Cleaning the scrubber procedure must be undertaken if the quantity of
precipitation in the NaOH scrubber is reaching the limit or the scrubber needs
changing every 6 months. The full scrubber cleaning protocol was developed as part
of the project and details are shown in Appendix C.
67
Chapter 5 Experimental setup
5.0 Experimental section

This chapter is divided into three different test setups. The first test setup
explains the laboratory samples and field samples received from Baker Hughes for
investigation of the surface film. The second test setup explains the procedure for the
sweet and sour experiments on natural pits, and the third test setup describes the sweet
and sour experiments on artificial pits.
5.1 Material used for study

The material used in these studies comprises X65 carbon steel. The specimens
for sweet experiment studies were embedded in a non-conducting resin. The average
chemical composition of the material is given in Table 5-1. The specimen was
isolated with an O-ring and connected with wire for electrochemistry measurement.
C Mn Si P S Cr Mo Ni Cu Sn
0.12 1.27 0.18 0.008 0.002 0.11 0.17 0.07 0.12 0.008
AI B Nb Ti V
0.022 0.0005 0.054 0.001 0.057
Table 5-1: Chemical analysis in % of carbon steel X65
5.2 Sample preparation procedure

Sample preparation for testing varied depending on the experiment, however,
in general, the process was divided into cutting, mounting, polishing and cleaning.
The materials were mounted using an automatic mounting press machine (Buehler
Simpliment 1000) in bakelite edge retaining mounting compound. The grinding and
polishing of the samples were carried out on a polishing machine (Buehler Beta
Grinder Polisher). The grinding and polishing were done using various grades of
silicon carbide paper (Buehler SiC paper) depending on the experiment. The polished
surfaces were cleaned with distilled water, rinsed with acetone and dried with
compressed air.
68
5.3 Corrosion testing setup

Electrochemical corrosion testing was used to investigate the corrOSIOn
behaviour of the material using the Princeton Applied Research Versastati3.
Electrochemical tests included linear polarisation scans and potentiostatic tests using a
conventional three-electrode cell for the electrochemical test setup. The setup
comprised a high temperature saturated AgiAgCl electrode as the reference electrode
and a platinum rod as the counter electrode and the sample as the working electrode.
In the linear polarisation test the experiments were performed at varIOUS

exposure times depending on the experiment. The polarisation measurements started
at 20m V more negative than the open circuit potential value and the measurements
ended at 20m V more positive than the open circuit potential value. The scan rate used
for measurements was lSmV/min (0.2SmV/sec). The potentiostatic test scans the
potential to 100m V in a positive direction from the open circuit potential and holds
the potential constant for 20 hours to activate and propagate the artificial pit. The
resulting current was recorded with time to observe the current behaviour.
5.4 In-situ camera setup

The in-situ visualisation assembly contained a camera system (Navitar), a lOX
long working distance objective (Mitutoyo), a lighting system and image monitoring
system, as described in the previous chapter. The camera recorded the surface image
every 20 seconds during the experiment. Thus, by using an image analysis system, the
film and pit growth could be analysed.
5.5 Experiment procedure for surface film investigation for sweet

and sour conditions.
This section describes the experimental procedure on sweet and sour
specimens for corrosion film characterisation; the results are presented in Chapter 6.
The sweet experiments were performed in a 3S0rpm stirred solution with 1 bar total
pressure of carbon dioxide gas with the temperature controlled at SO°c. The exposure
time varied from O.S hours to 72 hours in different experiments. Initially, 2 litres of
distilled water and I wt9'c sodium chloride (NaCl) were filled in the solution bottle
and it was purged with CO~ gas for 4 hours to remove any dissolved oxygen. To begin
69
an experiment, 850ml solution was tran sferred to a te st vesse l and was purged with
CO 2 for another 1 hour and the temperature was in creased to 50°C, re sulting in the
so lution having di ssolved oxygen at 30ppb and pH 4 saturation. The specimen with a
2
final exposed area of 2.094 cm and final grinding wi th 320 grit SiC paper was
prepared according to the sample preparation procedure. After that, the specimen was
submerged in the solution and the reference and counter electrode were added to the
system, as shown in Figure 5-1 .
Gas
Thermomete r Inlet
Gas
Outlet
Reference/
Working Counter
Electrode Electrode
Hot Plate
Figure 5-1 : Experimental setup for sweet tests.
Then , the syste m was connected with the electrochemical te sting in strument.
Durin t::>a the test, the vessel was sealed with continuou sly bubbling CO 2 and stirred at
350rpm usi ng a 2.5cm magnetic stirrer to equally mix the CO 2 gas with the so luti on
and simul ate a low flow ve loc ity. The experiments were performed at va ri ous
exposure times, as shown in Table 5-2 and all of the experiments were repeated twice .
70
Specimen Time (h)

1 0
2 0.5
3 1
4 2.5
5 4
6 8
7 24
8 72
Table 5-2: CorrosIOn munersIOn tIme for sweet tests at 50°C wIth 1% NaCI
The sour corrosion specimens were generated by Baker Hughes using X65
carbon steel in a solution made by mixing oilfield brine and hydrocarbon for the
purpose of surface analysis study. The corrosion tests for the sour specimens were
performed at Baker Hughes and then the specimens were sent to the University of
Leeds for the purpose of studying the sour film characteristic. This was in the early
stages of the project to allow for a sour rig to be set up in our laboratory. The
specimens for the sour corrosion tests were first pre-corroded for 2.5 hours in sweet
conditions then transferred to an autoclave for sour gas experiments in a field brine
and 1% field condensate. These experiments were conducted for 70 hours at various
temperatures to observe the differences of iron sulphide species on the surface film.
The temperatures of the sour corrosion specimens were as shown in Table 5-3. At the
and of the experiments, the specimens were rinsed with distilled water, dried with
compressed air and kept in a vacuum container
Specimen Corrosion descriptions

S09 Sweet pre-corrosion for 2.5 h and sour condition at 90°C for 70 h
S10 Sweet pre-corrosion for 2.5 h and sour condition at 15°C for 70 h
S 11 Sweet pre-corrosion for 2.5 h and sour condition at 15°C for 2 h
followed by 90°C for 70 h
Table 5-3: Sour expenment specImens-all speCImens pre-corroded In sweet
environment first
71
5.6 Experiment procedure for natural pitting test for sweet and
sour conditions.
This section describes the experimental procedure for sweet and sour
specimens for natural pitting experiments; the results of which are presented in
Chapter 7. The sweet experiments were performed in a solution stirred at 250rpm and
the temperature was controlled at 80°C, as shown in Figure 4.2 Chapter 4. Initially, 5
litres of distilled water and 10% sodium chloride (NaCl) were filled in a solution
bottle and purged with CO 2 gas for 24 hours to remove dissolved oxygen. To begin an
experiment, 800ml solution was transferred to a test vessel and purged with CO 2 for
another 1 hour and the temperature was increased to 80°C. The specimen was
prepared according to sample preparation procedure with a final exposed area of 1
2
cm and final grinding with 1200 grit SiC paper. After that the specimen was
immersed in the solution and the reference and counter electrodes were added to the
system. Then, the system was connected to the electrochemical testing instrument. On
the first set of tests, the blank tests were performed at various time durations, as
shown in Table 5-4 and were performed in triplicate to explore whether repeatable
pitting corrosion behaviour could be obtained. Then, in the second set of tests, two
different inhibitors - phosphate ester and imadazoline - were introduced at different
concentrations after 120 hours pre-corrosion and the pitting depths recorded after 150
hours. The concentrations of both of the inhibitors that were tested are shown in Table
5-5. During the test, the vessel was sealed with continuously bubbling CO 2 and stirred
at 250rpm using a 2.5cm magnetic stirrer to equally mix the CO 2 gas within the
solution.
Specimen Time (h)
1 2
2 24
3 70
4 96
5 120
6 150
Table 5-4: Natural pits blank test specimens at CO 2, 80°C, 10% NaCI, pH 5.65,
')+
1000ppm Fe- .
72
Specimen Conditions
1 IOppm phosphate ester
2 25ppm phosphate ester
5 IOOppm phosphate ester
8 10ppm imidazoline
9 25ppm imidazoline
10 50ppm imidazoline
12 IOOppm imidazoline
Table 5-5: Natural pit inhibitors test specimens at 150 hours, CO 2, 80°C, 109( NaCl,
pH 5.65, 1000ppm Fe 2+.
In order to achieve the desired conditions and obtain a protective film, several
steps were taken during the first 4 hours of the test. After 2 hours, the pH was
adjusted to 5.65 by adding a sodium bicarbonate (NaHC03) solution to reduce the
corrosion rate and initiate the pitting condition. After 4 hours, 1000ppm of iron
2
chloride (FeCh) was added to achieve a high concentration Fe + to generate a
protective iron carbonate film (FeC0 3). For the inhibitor test, after 120 hours various
concentrations of inhibitor were added to the solution to study the effect on pitting
propagation.
The sour experiments were performed on the sour rig, as shown in Figure -+-5
in Chapter 4. The tests were conducted at various temperatures, as shown in Table 5-
6, to observe the pitting behaviour under sour conditions. All the sour tests were
performed in lOlJ'c NaCI at 80°e. At the end of the experiments, the specimens were
linsed with distilled water, dried with compressed air and kept in a vacuum container
before surface analysis. In order to achieve the desired conditions at the beginning of
73
the test, pH was adj usted to 5.65 by addin g a sod ium bicarbonate (Na HC0 3 ) so luti on
and 1000ppm of iron chloride (FeCh) was added to ac hi eve a high co ncentrati on of
Fe 2+ .
Specimen Corrosion descriptions

1 10% NaCl , pH 5.65 , 1000ppm Fe -+ for 4 h
2 10% NaCI for 4 h
3 10% NaCl, pH 5.65 for 4 h
4 10% NaCI , pH 5.65 for 96 h
Table 5-6: Natural pIt te st specImens at 10% H 2S, 90% CO 2 , 80°C , 10% NaCI
5.7 Experimental procedure for artificial pitting test for sweet and
sour conditions.
Thi s section describe s the experimental procedure for sweet and sour
specimens for artificial pit experiments ; the re sults of which are presented in Chapter
8 and Chapter 9. The soluti on and specimen s were prepared the same as in the
previous section 5.6 at 80°C and 10% sodium chloride (NaC I). Artificial pits were
used in the se studies to evaluate the effectiveness of the inhibitor. For all speci mens
two artificial pits were generated by a microhardness indenter to m ake eac h pit 9f.l m
deep as shown in Figure 5-2. The specimens were finally rinsed with ace tone and
dried with compressed air before being pl aced in the specimen holder on the lid , as
shown in Figure 4-2 in Chapter 4. All pos sible care was taken to prevent surface
contamination of the sample .
't: 0
3
93
Figure 5-2: Artificial pit depth of X65 carbon steel before the test.
74
In order to achieve the desired conditions and obtain a protective film, several
steps were taken during the first 4 hours of the test. After 1.5 hours, pH was adjusted to
5.65 by adding a sodium bicarbonate (NaHC0 3 ) solution to reduce the corrosion rate and
initiate the pitting condition. After 3 hours, 1000ppm of iron chloride (FeCh) was added
to achieve a high concentration Fe 2+ to generate a protective iron carbonate film
(FeC0 3). After 3.5 hours various concentrations of phosphate ester and imidazoline
were added to the solution to study the effect on artificial pitting, as shown in Table 5-
7.
Specimen Conditions
1 Blank
9 25ppm imidazoline
Table 5-7: Artificial pits inhibitor test specimens at 150 hours, CO 2, 80°C, 10% NaCI,
pH 5.65, 1000ppm Fe 2+.
Corrosion testing was performed usmg DC Linear Polarisation Resistance

(LPR) after every step to monitor the corrosion rate and after 4 hours the specimen
was immersed in the solution and achieved the desired condition; potentiostatic tests
were carried out. These experiments were conducted for 24 hours and at the end of the
experiment, the specimens were rinsed with distilled water, dried with compressed air
and kept in a vacuum container before the surface analysis.
The sour experiments were performed on the in-situ sour ng, as shown in
Figure 4-5 in Chapter 4. The solution, specimens and artificial pits were prepared the
same way as for in the sweet experiment setup at 80°C and 109c sodium chloride
(NaCI). Various concentrations of nonoxynol-6 phosphate and poly alkyl pyridine
75
inhibitors, as shown in Table 5-8, were added in the test vessel at the beginning of the
test to study the behaviour of the inhibitors.
Specimen Conditions
1 Blank
2 25ppm nonoxynol-6 phosphate
9 25ppm poly alkyl pyridines
... . .
Table 5-8: ArtIfIcIal pit mhibItor test speCimens at 24 hours, at 10% H 2S, 90<;'( CO 2 ,
80°C, 10% NaCI
5.8 Post test analysis

Various surface analysis techniques were used in this study to measure the pit
depth, investigate the corrosion film and understand the inhibitor interaction. The pit
depth measurement was carried out using white light interferometry, profilometry and
optical microscopy. The topographical detail measurement was carried out using
secondary electron microscopy, focused iron beam and atomic force microscopy. The
chemical characterisation was carried out using the energy dispersive X-ray
technique, X-ray photoelectron spectroscopy and fourier transform infrared
spectroscopy.
5.8.1 Talysurf5 profilometry

A talysurf5 contact surface profilometer (Taylor and Hobson) was used in this
study to measure the surface profile of pre-test and post test specimens and to measure
the pitting depth. The profilometer uses a software tool, Talymap Gold, which gives
3D and 2D data after mapping the surface and provides significant data to identify pit
depth.
76
5.8.2 White light interferometer

A white light interferometer (Veeco WYKO) has high magnification and high
resolution non-contact surface profilometry. The pit depth, which has a very rough
surface, was carried out using this surface analysis technique. This technique IS
capable of measuring the objective in the magnification range from 2X-SOX.
5.8.3 Optical microscopy

A Nikon optical microscope was used for viewing the corrosion surface and
pit depth surface. The microscope was capable of measuring surfaces with
magnification between lOX to SOX magnification. The microscope uses a software
tool to view surface images for additional image processing.
5.8.4 Secondary Electron Microscopy and Energy Dispersive X-ray

Analysis (SEM-EDX)
SEM-EDX (Phillips XL 30 instrument) is a surface analysis technique to
characterise the surface morphology and chemical characteristics of the surface film
under vacuum conditions. An SEM scans the surface of the specimen with an electron
beam to study the shape and form of structure on the surface. This technique is
extremely useful for studying and characterising the morphology of surface corrosion
film or cross-section corrosion film. For this study, all specimens were scanned using
input voltage 20KeV. EDX techniques were able to analyse the constituent elements
present on the surface. The chemical elements analysed in this study were carbon (C),
iron (Fe), oxygen (0) and sulphur (S).
5.8.5 Atomic Force Microscopy (AFM)

AFM instrument (Veeco) was used to investigate topographical structures and
provide a high resolution and high magnification topographical measurement in
ambient conditions. There are three common modes used in the AFM techniques -
contact mode, non-contact mode and tapping mode. For this study, the AFM contact
mode was used in which a constant force was maintained between the probe and
specimen sUlface and probe raster scans on the surface to obtain topographical details
of the corrosion film [71].
77
5.8.6 Focused Ion Beam (FIB)

FIB (Nova 200 NanoLab) with a high-resolution field emission gun scanning
electron microscope (FEGSEM) was used to investigate the cross-sectional surface
detail at the very early stages corrosion film formation. A platinum layer was coated
on the top of the area of interest to protect the surface from any damage from
irradiated high energy Ga ion during the cross-section ion bombarding process. For
this study, the specimens after 0.5 hours corrosion were examined to measure the
thickness of the corrosion film.
5.8.7 X-ray Photoelectron Spectroscopy (XPS)

XPS analysis provides information on the elements present and their chemical
species on the surface film [177-181]. The specimens were cleaned using acetone to
remove contaminations before doing XPS analysis [182]. The specimens were then
mounted on the sample holder and placed in an XPS chamber to proceed with
analysis. The calibration of XPS spectra was carried out on the area of interest to
achieve maximum intensity of XPS signal [183]. The carbon peak was selected to
calibrate XPS spectra and achieve maximum intensity. Then, the survey scan spectra
was acquired for each sample. Figure 5-3 shows the survey scan for the bank
speCImen.
Jl~
___ .--- _ L - - - , - _ L L_ _ _ _--L_-~___.__---L-L--_,___--..1l---__'__'t'

j eo.'.
Bindm~ En..~· (e\')
Figure 5-3: XPS survey scan for X65 carbon steel surface before the test.
78
The survey scan provides the infonnation concerning the elements that are
present in the area of interest. Following acquisition of the survey scan spectra, the
acquisition of individual elemental scan was carried out for the elements observed on
the surface and the elements expected on the surface. Argon ion bombardment of the
surface was carried out to enable depth profiling of the specimen and provide the
distribution of elements as a function of depth into the sample [77]. An area of 500
11 m x 500 11 m in corrosion film was analysed using a monochromatised Al K[a]
source in the XPS. The spatial mode was chosen to acquire the spectra and argon
etching was performed using an ion gun set at beam energy 3 ke V and lilA set at 0
second and after 60 seconds. CasaXPS software was used to fit the curves on the
acquired individual elemental peaks and the quantitative analyses of the peaks were
performed using peak area sensitivity factors [184, 185]. The area of individual
elemental peak was selected and curve fitting was perfonned keeping the area and full
with half maximum consistent for that peak. Doublet peaks for Fe 2P3/2 were also
fitted. The form of peaks used in all fitting procedures was Gaussian-Lorenzian [77].
Shirley background subtraction was used for all quantification to remove the data to
symmetric shape to represent quantification results [2, 48, 185]. The relative
sensitivity factor used in the software is 1 to compare the peak intensities.
5.8.8 Fourier Transform InfraRed (FTIR)

FTIR measurements were carried out with Perkin Elmer model spotlight 400.
FTIR is a technique used to obtain an infrared spectrum [186-189]. FTIR has been
used in this study to identify inhibitors that are tenaciously adsorbed to steel surface
and corrosion film. A point mode operation and reflectance sampling mode were used
in this study. IR reflectance spectra in the region 600 to 4000 cm- I were collected. A
background reflectance of a gold electrode was perfonned as a reference before
measurements were made on all test specimens. The average of ten scans was
recorded for each specimen spectra. Spectrum software was used to analyse the FTIR
data obtained. The individual data line was further processed by data tune up and a
smoothing process to reduce the data noise.
79
5.9 Inhibitors
Four different single inhibitor components from Baker Hughes were designed
to inhibit localised corrosion in this study [190]. Phosphate ester and imidazoline
were used in the sweet condition test and nonoxoxnol-6 phosphate and poly alkyl
pyridines were used in the sour condition test.
5.9.1 Phosphate ester inhibitor

Alcohol ethoxylate phosphate, or the genenc name used in this study -
phosphate ester - is a 5 mole ethoxylated iso-tridecanol. This is made by trimerisation
of n-butene and then hydroformylation (oxo synthesis) of the olefin with carbon
monoxide and hydrogen to produce an isomeric mixture of primary isotridecyl
alcohols with a branched alkyl chain [190]. Then this mixture was reacted with P20S
to give a nominal structure, as shown in Figure 5-4 [190], and subsequently diluted in
10% methanol for use in the sweet condition test.
H3C~
CH 3
Figure 5-4: Nominal structure of phosphate ester inhibitor [190]
5.9.2 Imidazoline inhibitor

Diethylenetriamine alkly imidazoline, or the generic name used in this study -
imidazoline - is the reaction product of tall oil fatty acid with diethylenetriamine
(1: 1), which gives a nominal structure, as shown in Figure 5-5 [190]. Then this
mixture was diluted in 10% isopropanol with 2% acetic acid for use in the sweet
condition test.
n
N ~ N~
'-. . ./
/'--.....
~ NH,
Y R
R=C17
Figure 5-5: Nominal structure of imidazoline inhibitor [190]

80
5.9.3 Nonoxoynol-6 phosphate inhibitor

Nonoxoynol-6 phosphate inhibitor is a 6 ethoxylated p-nonylphenol, which is
reacted with P20 S to give a nominal structure, as shown in Figure 5-6 [190], and then
diluted in 10% methanol for use in the sour condition test.
Figure 5-6: Nominal structure of nonoxoynol-6 phosphate inhibitor [190]
5.9.4 Poly alkyl pyridine inhibitor

Poly alkyl pyridine inhibitors are a waste stream that contain many alkyl
pyridine components, some of which are shown in Figure 5-7 [190]. Each of the
pyridine components could quaternise the benzyl chloride, as shown in Figure 5-8
[190]. Then this mixture was diluted in 10% methanol for use in the sour condition
test.
(1) (3) (el
(6. m (9.
~ ~
(lOJ (Ill (12)
Ji'~ ~
(lJ) (1~ (151
~~ ~
(16) (1n (1B)
Figure 5-7: Nominal structure of poly alkyl pyridines inhibitor [190]

81
CI
Figure 5-8: Nominal structure of pyridine components quaternise the benzyl chloride
[190]
82
Chapter 6 Characterisation of the surface film formed from sweet

and sour corrosion
In this chapter the results of surface analysis in sweet and sour environments
are presented. Surface analysis was performed using Scanning Electron Microscopy
(SEM), Energy Dispersive X-Ray (EDX), X-Ray Photoelectron Spectroscopy (XPS),
Atomic Force Microscope (AFM) and Focus Ion Beam (FIB-SEM) to investigate the
compositional and morphological difference of corrosion product films grown on X65
carbon steel in the early stages of sweet and in sour conditions. This Chapter is
divided in two stages: the first stage studies the growth of sweet films under different
exposure times. The second stage is to understand the corrosion films under sour
conditions after 2.5 hours sweet corrosion. The objective of this chapter is to
understand the corrosion films morphology and corrosion species in sweet and sour
conditions and understand the film breakdown phenomena.
6.1 Corrosion current measurement

6.1.1 Sweet experiments
The sweet experiments were performed in 850ml, 1% sodium chloride at 1 bar
total pressure of carbon dioxide gas with the temperature controlled at 50°C. The
exposure time varied from 0.5 to 72 hours in different experiments. Electrochemical
corrosion measurements using DC linear polarisation resistance were carried out to
monitor the corrosion rate during sweet film formation. The corrosion rates recorded
ranged between 3 mm/yr and 4 mm/yr. Figure 6-1 shows the corrosion rates for tests
from 0.5 to 8 hours immersion. It shows that the corrosion rate started in the range
between 2.6 mm/yr and 2.8 mmfyr in the first 26 minutes and then increased to the
range between 3 mm/yr and 4 mm/yr, and was maintained at this rate until the end of
the 8-hour test. This shows that the film formation process takes about 52 minutes to
reach steady state conditions at this temperature and in this solution. Figure 6-2 shows
the corrosion rate for longer time tests at 24 hours and 72 hours. The corrosion rates
for the longer duration tests show similar behaviour in the first 52 minutes. The
corrosion rates range between 3 mm/y and 4 mm/yr, and stays at this rate until the end
of the 72-hours test.
83
4
~
....
>-.
E 3
E
'-"
Q.)
<-oJ
C'j
.... 2
..=
0. .
rJl
0
1
t::
0
U 0
0 2 3 4 5 6 7 8
Time (h)
-+- O.5h ~ lh 2.5h ~ 4h ~ 8 h
Figure 6-1 : Corrosion rate versus time for short tests on X65 carbon in CO 2-saturated
1% NaCI brine at 50°C and 1 bar total pressure.
4
....
----
>-.
E 3
E
'--'
())
.....
C'j
.... 2
t:
.0v.;
0
l::
0
U
0
0 10 20 30 40 50 60 70
Time (h)
...... 24h - ' - 72h
Figure 6-2 : Corrosion rate versus time for long te sts on X65 carbon in CO 2-saturated
I % NaCI brine at 50°C and 1 bar total pressure
This result I S In agreement with Crolet et ai. who obtained 3.3 mm/yr
corrosion rate at pH 4, 22°C and saturated CO 2 [191] . The corros ion rate
measurements show that the film formation under thi s condition is non-protective .
Thi s is supported by Schmitt et aI. , which shows that the typica l films formed at 50°C
with saturated C02 typica lly contains fla ws and inhomogeneties [62].
84
6.1.2 Sour experiments

The sour specimens were prepared by the researcher at Baker Hughes [190]
for the purpose of the surface analysis for thi s project. Thi s was in the early stages of
the project while the H2S rig in our laboratory was being set up . The specimens were
prepared in 1% NaCl for 2.5 hours in sweet conditions and then transferred to an
autoclave for sour conditions in Shell pearl HTDS brine and 1% field condensate for
70 hours at 15°C, 90°C and mixed temperatures starting at 15°C and increasing to
90°C after the specimen was immersed. Figure 6-3 shows the corrosion rate s for
specimens under sour conditions after 2.5 hours pre-corrosion in a sweet environm ent.
0.4
...>-.
---.
E 0.3
.... --- -- --- ~
E
'--' - - --~
<l.l
~
0.2
...
c
0
0.1 .... ...... .....,. .....,.
....... ......
(/)
0 ....... ..... ....... ..... .... ....... ........ .... .... ..... .... ....... ...... r-
t
0
U 0.0
60 62 64 66 68 70
Time (h)
Figure 6-3 : Corrosion rate versus time at 3.3 bar H 2S and 5.0 bar CO 2 at various
temperatures [190]
The specimen at 90°C has the lowest corrosion rate at 0.08 mm/yr after the
first hour and the specimen at 15°C has a slightly higher corrosion rate at 0.25 mrn/yr.
Both specimens maintained their corrosion rate until the end of the test and both show
that the film that form s under thi s sour condition is a semi-protecti ve type [4, 5, Ill] .
The specimen at 90°C has a greater protecti ve film due to the hi gher temperature and
its effect on the characteristics and morphology of the film [5]. It is interesting to note
that the corrosion rate of the speci mens with mi xed temperatures was sub stan ti all y
higher than the spec imens at 90°C and 15°C which was at 0 .3 mrn/yr.
85
6.2 SEM analysis

6.2.1 Sweet experiments
The morphology of the pre-corrosion surface is shown from Figure 6-4 to
Figure 6-11. It can be seen that the corrosion deposits grow with time, which is in
agreement with electrochemical measurements conducted during the corrosion test.
Figure 6-4 shows the specimen surface before the test. The corrosion film starts
growing on the surface after 0.5 hours by eradicating the polishing mark on the
surface, as shown in Figure 6-5. It can be seen that the surface darkens due to the film
building up on the surface after 1 hour, as shown in Figure 6-6. After 2.5 hours the
corrosion layer formed on the metal surface is compact and quite homogeneous,
however, the film is getting thicker, as shown in Figure 6-7.
After 4 hours corrOSIOn, the corrOSIOn films starts to create a porous

morphology with the Fe3C network frame structure observed on the surface, as shown
in Figure 6-8. The corrosion product build-up follows the preferential carbide
network, which can be seen until 8 hours, as shown in Figure 6-9. The film build up
process continues and gets thicker after 24 hours and 72 hours, as shown in Figure 6-
10 and Figure 6-11. It can be seen that the morphology of the film at 24 hours and 72
hours is porous and non-uniform; some of the unfilled regions between the surfaces
could be influenced by the carbide layer on the surface, as observed by Lopez et al.
[1].
A cross-section analysis was carried out to measure the thickness of the film.
The specimens were mounted in another non-conducting resin and the cross-sectional
surface was polished with silicon carbide paper (320, 500, 800 and 1200 grit), and
finally polished to a 111m diamond finish. These were cleaned with acetone and
distilled water and finally dried. The cross-sectional analyses were performed for
samples 0.5 hours, 2.5 hours and 24 hours. Cross-sectional analysis observed an
average thickness of 311m on the 0.5 hours corrosion, as shown in Figure 6-12 and
411m on the 2.5 hours corrosion, as shown in Figure 6-13.
86
Figure 6-4: SEM image of the specimens before the experiments
Figure 6-5 : SEM im age of the sweet pre-corrosion specimen s at sooe after 0.5 hours
87
Figure 6-6: SEM image of the sweet pre-corrosion specimens at SO°C after 1 hour
Figure 6-7: SEM image of the sweet pre-corrosion specimens at SO°C after 2.S hours
88
Ele ctr on Image 1
Figure 6-8: SEM image of the sweet pre-corrosion specimens at 50°C after 4 hours
Figure 6-9: SEM im age of the sweet pre-corrosion specimens at 50°C after 8 hours
89
Figure 6-10: SEM image of the sweet pre-corrosion specimens at 50°C after 24 hours
Figure 6-1 1: SEM image of the sweet pre-corrosion specimens at 50°C after 72 hours
90
The external part of the corrosion film seems to be den ser and more compac t
but has poor contact and bonding to the metal surface . The film thickness gre w
thicker, to 23f..lm after 24 hours, as shown in Figure 6-14.
Figure 6-12: SEM image of the cross-section of sweet pre-colTosion at 50°C after 0.5
hours
~llI n
Figure 6-13: SEM image of the cross-sec ti on of sweet pre-colTosion at 50°C after 2.5
hours
91
20um
Figure 6-14: SEM image of the cross-section of sweet pre-corrosion at 50°C after 24
hours
The morphology after 24 hours shows that the ex tern al part of the film s see ms
to be porous and non-hom ogeneous with the internal part appearing to be more dense
and compac t [1]. Thi s shows that compact and denser depos its grow in the first
in stance foll owed by the growth of a porous layer in the film , which made the film
non-unifo rm . Thi s caused the result to be in agreement with the low corrosion rate at
2.6 mm/yr to 2. 8 mm/yr in the fi rs t hour when the film is controlled by co mpac t and
dense deposits, which could be iron carbonate. Then, the corrosion rate increases to
the range between 3 mm/yr to 4 mm/yr when the porous layer is present in the fil m,
w hi ch could be a mi x of iron carbonate and iron carbide and caused the fil m to be of
the not pro tecti ve type [5] .
6.2.2 Sour experiments

In sour conditi ons, the microstructure pattern that is observed on the spec im en
IS diffe rent at high and low temperatures. T he sour corrosion deposits at hi gh
te mperature are composed of two diffe rent layers, as shown in Figure 6-15 . T he first
92
layer depo sit grows uniformly all over the materi al interface and the second layer
grows in scattered domain s on the first layer, as observed by Svenningse n et al. [1 27] .
The film s in low temperature sour corrosion look different because the pre-corrosion
film can still be seen as the base film and a new corro sion layer grows sporadi cally on
top of this base film , as shown in Figure 6-16 .
Figure 6-1S: SEM image of the sour corrosion specimens at 90°C for 70 hours
Fi baure 6-16 : SEM image of the sour corrosion specimens at IS oC afte r 70 hours
93
It seem s that the morphology of the resulting film for mi xed temperature specimens is
dominated by the nature of the low temperature pattern , as shown in Figure 6-17 . The
specimen is charging, which could be due to it being non-conducti ve. It is interesting
to note that the sour corro sion film provides good protectiveness in a constant hi oh or
o
low temperature environment. Thi s is in agreement wi th Sun et al. who observed a
weak temperature dependence on the protecti veness, but suggested that the
protectiveness is dependent on longer exposure time [4] .
Figure 6-17: SEM image of the sour corrosion specimen s at 15°C for I Sl hour and
increased to 90°C after 70 hours
6.3 FIB/SEM analysis

The Focused Ion Beam and SEM cross-sectional technique were performed
for the sample exposed for 0.5 hours to observe the film thickness. Figure 6-ISa and
Figure 6-ISb show the platinum laye r that was placed onto the surface to protect the
top surface during the process of helium etching the cross-section. It can be seen th at
the average film thickness of 1.311m was observed on the 0.5 hours specimen , as
shown in Figure 6-18c.
The morph ology is shown to be denser and more co mpac t at the fi lm intelface
and so me porous structure is more visible at the base of the film adjace nt to the
94
substrate . The porous structure in the film sho ws the corros ion initi ati on stage with
small spots generated at the internal part of the film , which could be du e to the
formation of Fe3C as a result of the anodic reacti ons, as shown by the FIB-SEM
topography image after O.S hours corrosion in Figure 6-19 . The observati on of O. S
hours corrosion film specimens from the SEM cross-sectional method is not very
clear due to the small film thickness. At higher magnification the FIB tec hnique
reveal s that the corrosion film has a lower thickness and that the film has a good
contact and bonding to the metal surface.
a) b)
, Surfa ce
"p' H, · , IJ : . . :1 .,~,.; ..... I f'· .... . "' ] :. - '~' ---

E: T. 'x. . " . ~_I), /.., ' "'''T' • L: . ~~u ......: 11. • • : ,,',. · , 1 .... -- . •
c)
PI(l l lnllm
Figure 6- 18 : FIB/SEM Image of the cross-section for sweet pre-corrosIOn at SO°C
after O.S hours

95
Figure 6-19 : FIB-SEM image of undissolved Fe3C after 0 .5 hours for X65 carbon
steel in CO2 saturated 1% NaCI brine at 50°C and I bar total pressure
6.4 AFM analysis

The morphology of early stage sweet cOITosion films was also observed by a
contact AFM method. Surface morphologies of uncoIToded and cOIToded specime ns
are compared to study the thickness and roughne ss of the film . The image in Figure 6-
20 indicates that the corrosion deposits are increasing with time . The thickne ss of the
0 .5 hour film is estimated to be 1.37Ilm, which is in agreement with the thickness
obtained by FIB/SEM. The roughness and thickness of the film increased wi th the
exposure time, as shown in Table 6-1 . The thickne ss of the film also increases when
the corrosion rate increases, as shown in Figure 6-21.
The difference between the peak to valley height is increasing showing that
the film growth due to the increase of corrosion rate generate s a non-uniform film on
the surface . The difference between the uncoIToded and 0.5 hours specimen is very
small , which could be because the film seems to be den ser, and more compact and
smooth in the early stages. Thi s could be supported by the lower cOITos ion rate
observed at 0 .5 hours during the cOITos ion initiation stage . The fi lm roughness starts
increasing after 1 hour at 84.4nm to 138.3 nm after 4 hours due to the deposit growth
on the film . Thi s make s the surface fluctuation increase indicating non-h omoge neous
96
film growth on the external part of th at fi lm whi ch makes the film co ntinue
unprotec ted .
Time (hour) 0 0.5 1 2.5 4
Thickness, t (/lm) 0 .7 1.4 1.5 1.8 2.1

IA verage roughness, Ra (nm) 78 .9 68 .8 84.4 11 2.8 138 .3
!Max. Peak to valley height, Rt (nm) 418 .3 487 .2 622.7 667 .8 993 .5
Table 6-1: AFM analysis for sweet pre-corrosion specimens.
a)Oh
I..I.IJIT
1 8fJIll
Figure 6-20: AFM image s of the sweet pre-c orrosion surface after difference ex posure
times at 50°C. a) 0 hour ; b) 0.5 hours; c) 1 hour ; d) 2.5 hours ; e) 4 hours
97
2.5
2.0
----
E
::l.
~
1.5
v;
V)
Q)
c 1.0
.;.::
u
l:-
~ 0.5 :"'-" .1
0.0
1.8 2.3 2.8 3.3 3.8
Corrosion rate (mm/yr)
Figure 6-2 1: Film thickness versus corrosion rate versus time for X65 carbon in COJ
saturated 1% NaC I brine at 50°C and I bar total pressure -
6.5 EDX analysis

The nature of the surface fi lm can be defined more accurate ly by observing the
relative compositions of elements carbon , oxygen and iron performed by EDX . Tabl e
6-2 shows the composition of the elements in the pre-corrosion laye rs.
Time (h our) 0 0.5 1 2.5 4 8 24 72

Cwt % 1.8 2.5 2.4 4.2 5.2 6.4 8.2 9.2
O wt % 0 0 3.6 5.3 5.2 5.9 14.5 18 .8
lYe wt % 98.2 97.5 94.0 90.5 86.5 87 .8 77.3 72.0

Table 6-2: Relative element composition of sweet pre-corrosion layers
It was found that the percentage of carbon and oxygen in the corroded layers
is higher than for the uncorroded specimens, as expected [48] . The reduction of iron
and increment of oxygen and carbon is time dependent becau se the hjghe st percentage
of iron was found in the 0 .5 hours specimen, which has the lowest immersion time
and the lowest iron was found in the 72 hours specimen , which has the longest
immersion time . The increasing of C and 0 and decreasing of Fe is sugge sted as the
result of iron carbonate film growth [42] . Figure 6-22 show s that the film thi ckness
increases as a result of the iron content decreasing wi th time . Thi s reaction turn s to a
linear relati on after I hours exposure, as sho wn in Figure 6-23 . After 24 hours, Figure
6-24 shows th at the morph ology of the film re vea ls two di stinct phases consistin g of
98
fl at dark grey regions, which are porous fi lm wi th scattered whitish flake s type film
around the surface . EDX data shows that the percentage ratio of Fe :C:O for the
w hiti sh fl akes area is 60:9:26, whi ch indi cates a FeC0 3 fil m and the porous film area
shows that the percentage ratio of Fe: C:O is 88:5:4, whic h indicates a Fe3C film . Thi s
is in agreement with Ruzic et a1. who in their studies prove th at the EDX content of
the whiti sh flakes type film is identified as a pure FeC0 3 type film [42] .
100 2.5
98 ,..
,-
<J6 2 -<
-'-
c 94
0 1. 5 '/"C
(U 92 ' /"C
'u
~
,..
90 1 ~
88 (J
86 0.5 ;:::l
--<
84 f--o
a
0 1 2 3 4
Tllllc (Hom )
Figure 6-22: Film thickness and Fe% content versus time fo r X65 carbon steel in CO 2
saturated 1% NaCI brine at 50°C and 1 bar total pressure
100
11 hour J
_/
98
96
• JI 4 hours lI
94
~
.., 92
u..
90 • ~
88
86 •
84 -
o 0.5 1 1.5 2 2.5
Film Thi ckness ( ~m )
Fi gure 6-23 : Film thickness versus Fe % content for X65 carbon stee l in CO 2 saturated
1% NaCI brine at 50°C and 1 bar total pressure
99
Figure 6-24 : SEM im age after 24 hours fo r X65 carbon steel in CO2 saturated 1%
NaCI brine at 50°C and I bar total press ure
Tabl e 6- 3 shows the relati ve composition of elements in sour corrosion layer.

It shows that the carbon and sulphur were enriched in the specimen at 90°C and 15°C
providing good corrosion protecti on. The oxygen percentage is the same for all
specimens. It is interesting to note that the carbon to oxygen rati o is hi gher in the 0.5
hours sweet spec imen and the sour specimen at 90°C and 15°C, which have a
simil arity in the low corrosion rate.
lTemp. 90°C 15°C 15°C to 90°C

Cwt % 8.6 7.1 4.7
Owt % 25.4 27 .5 26.3
~wt % 12.7 7.1 0.9
!Fe wt % 53 .3 58 .3 68. 1
Table 6-3: Relati ve compositi on of elements in sour corrOSIOn layers
100
6.6 XPS analysis

Surface films on se lected corroded specImens are analysed using X-ray
Photoelectron Spectroscopy (XPS). Survey spectra were recorded for all specimen s
and high-resolution scans were conducted over the follo wing regi ons of interest; CI s
and Fe 2p. Sputtering of the sample surface was performed with an argon ion gun and
were measured after 0 and 60 seconds of Ar+ sputtering. Casa XPS software was used
to fit the curves on XPS peaks and the XPS handbook was used to find the chemical
species at the respective binding energies [177-180] .
6.6.1 Evolution of C Is peaks

XPS analyses on carbon spectra for 0 hour specimens (as-polished surface) ,
2.5-hour sweet specimens and sour specimens are shown in Table 6-4 to identify the
presence of cementite and carbonate on the films.
C Is Oh 2.S h sweet 70 h sour

Peak Element polished surface at SO°C at 90°C
BE(eV) Wt % BE(eV) Wt % BE(eV) Wt %
I Graphitic/
Hydrocarbonate 285.72 100 285.62 66 285.47 72 .6
II Fe3C - - 281.78 4.5 282.29 3.6

III FeC0 3 - - 287.8 17.2 288.68 13 .6
IV FeC0 3 - - 289.81 12.3 291.38 10.3
Table 6-4: Curve fIttmg analYSIS for Cis spectrum.
Figure 6-25 shows the Cis spectra curve fitting for the as-polished surface ,
which revealed a carbon peak at 285.72e V that represents the carbon atom in graphitic
or hydrocarbonate absorbed in the surface layer [2, 48 , 152] . For specimens after 2.5
hours sweet corrosion, Figure 6-26 shows the curve fitting for Ci s spectra at
285 .62e V , which represents the same carbon in graphitic or hydrocarbonate absorbed
peak as-polished surface [2, 48 , 152]. A new peak is also re vealed at binding energies
of 287.80eV and 289 .81eV corresponding to pure iron carbonate and at binding
energies of 281.81 e V corresponding to cementite [2, 48 , 152].
101
C Is
Zl 8
0...
U
~ S6
B inding Energy (eV)

Figure 6-25 : Surface scan of C Is spectrum and curve fitting for 0 hour
C [,
1
70 x 10
~
60 u
50
40
(fJ
p...
0
30
20
10
292 290 288 286 284 282 280

Binding Energy (eV)
Figure 6-26 : Surface scan of CIs spectrum and curve fitting for 2.5 hour swee t pre-
corrosion at 50°C.
102
The surface weight concentration analysi s shows that a mixed type of film was
formed on the surface with iron carbonate as the mai n spec ies at 29 .5% compared to
cementite at 4.5 %. A longer etching time is needed to obtain a stronger iron carbide
peak because iron carbonate mostly grows on the film surface. These re sults are in
agreement with the SEM images, which sho w the film morphology of the mixed iron
carbonateliron carbide.
The sour specImen Figure 6-27 reveal s the peaks at binding energIes of
288 .68e V and 291.38e V, corresponding to pure iron carbonate, and the peaks at
binding energies of 282.2geV, corresponding to cementite [2,48 , 15 2]. Thi s re veals
that a mixed type of film was formed on the surface with iron carbonate as the main
species at 23.9 % compared to cementite at 3.6%. The surface weight concentrati on of
iron carbonate species is lower compared to the 2.5-hour sweet corrosion specimens.
This conforms to the presence of iron carbonate and iron carbide film in thi s sour
specimen . The presence of iron sulphide film will be investigated by observing the
iron Fe 2P3/2 spectra.
CIs
25
20
(/) 15
p..
o
III
~94 290 2SS JS6 284 280

B inding Energy (eV)
Figure 6-27 : Surface scan of CI s spec trum and curve fitting for the sour corros ion
after 70 hours at 90°C

103
6.6.2 Evolution of Fe 2P3/2 peaks

XPS analyses on Fe 2P312 peak for O-hour specimens (as-polished surface), 2.5-
hour sweet specimens, sour specimens at 90°C and sour specimen at ISoC are shown
in Table 6.S to identify the presence of Fe, Fe 2+ and Fe 3+ on the surface and
subsurface. The Fe 2P312 peak shows the doublet for the O-hour (as-polished surface)
specimens before and after 60 seconds etching, as shown in Figure 6-28. It shows that
a clear Fe peak can be obtained after 60 seconds etching, estimated to be about Snm
below the film, which removes iron oxide on the surface probably due to air
contamination during sample preparation [48, 77, 192]. It has been observed by Sakai
et al. that the etching rate of polystyrene by the gun was determined to be Snm/min
[192]. The curve fitting for the as-polished surface after 60 seconds etching is shown
in Figure 6-29. The peak at 707.39 represents a combination of iron as iron metal and
cementite on the surface [177, 181]. It has been reported by Li et al. that the binding
energies of Fe 2P3/2 for cementite and iron are at 707.3eV and 707.0eV, respectively
[181]. The binding energy of cementite is 0.3e V higher then iron, which is very small
to be properly identified. The presence of oxidised species at 709 .80e V and 711. 98e V
in the film could be attributed to a mixture contribution from the presence of Fe 2+ and
3
Fe + in the form of FeO and Fe 203 due to the contamination by surface reaction with
the atmosphere during the sample preparation [1, 2 112, 181].
Fe 2P3/2 Oh 2.5 h sweet 70 h sour 70 h sour
Element polished surface at 50°C at 90°C at 15°C

Peak BE(eV) Wt% BE(eV) Wt% BE(eV) Wt% BE(eV) Wt%
I Fe/ Fe3C 707.39 55.9 - - - - - -
I Fe/ FeS - - - - 707.58 25.6 - -
II FeO-Fe20 3 709.80 27.2 710.39 84.9 710.09 42.7 710.40 53.3
III Fe203 711.98 16.9 - - - - - -

IV FeS - - - - 712.47 22.6 712.47 8.8
V FeC0 3 - - 714.83 15.1 715.48 9.1 714.23 19.9
VI Fe203 - - - - - - 717.81 18
Table 6-5: Curve fIttmg analysIs for Fe 2P3/2 spectrum at 60s

104
Fe
,
~:O
~ - ________________________________________________ ~
." l
'c
I-Osl
~
B i uding Energy (e \ ')

Figure 6-28: Sputtering of Fe 2P312 spectrum for O-hour (as polished surface)
specimen at Os and after 60s etching.
Fe'
Binding Energy (e V)
Figure 6-29 : Surface scan of Fe 2P 3/2 spectrum and curve fitting for O-hour (as-
polished sample) after 60s etching.
lOS
Figure 6-30 shows the 2.S-hour sweet specimen spectra, the peak at 714.3eV
represents iron carbonate and the peak at 710.3geV in the binding energy covered by
FeO and Fe203 [48, 112]. It has been reported by Lopez et al. that the decomposition
process that iron carbonate may undergo at temperatures below 100°C will finally
lead to FeO and Fe203 [48]. Figure 6-31 and Figure 6-32 show the Fe 2P312 spectrum
for the sour specimen at 90°C and the sour specimen at lS°C. The binding energy at
707.S8eV for 90°C sour specimens indicates the presence of FeS2, which is pyrite
[171, 177]. It has been reported by Neal et al. that pyrite was observed at binding
energy 707.SeV [171]. It is interesting to reveal that the pyrite peak is only present in
the 90°C sour specimens and absent in the ISoe sour specimen. Smith's review
indicates that pyrite formation is influenced by high H2S activity and the presence of
elemental sulphur, as shown in Figure 3.10 in Chapter 3 [109, 113]. This shows that
the higher temperature influences the solubility and rate of kinetic reaction, which
increases the H 2S activity that leads to the formation of pyrite at 90°C [20, 109, 110,
113, 122].
The binding energy at 712.47eV on both specimens also indicates the presence
of FeS on the surface [177]. The area under the curve fitting indicates that sulphide
species is likely to grow at high temperature with a surface weight concentration of
48.2% compared to 8.8% at low temperature. This is supported by Kvarekval et aI.,
who show that iron sulphide is more likely to form at higher temperatures compared
to iron carbonate [122]. This is because the solubility of FeS increases when
temperature increases [110, 122]. A peak at 71S.48eV for 90°C sour specimen and at
714.23eV for ISoe sour specimens shows the presence of iron carbonate. The higher
percentage of oxidised species observed in the low temperature sour sample could be
due to the dominant iron carbonate [48, 112]. The reaction of Fe ions and excess H2S
subsequently results in ferrous sulphide production and effect the oxidation, this will
affect the quantitative analysis on the curve fitting, however literature report that ion
bombardment can cause various physical and chemical change on the surface and
underlying layers such as compositional mixing and crystalline structure [48, 171].
Figure 6-33 summarise the XPS results and shows that after 2.S hour sweet
corrosion, the corrosion films were iron carbide and iron carbonate. Then, after 70
hours sour test, the sour corrosion product growth on top of sweet corrosion product.
106
III :L
Binding Energy (e\')

Figure 6-30: Surface scan of Fe 2P3/2 spectrum and curve fitting for 2.S-hour sweet
pre-corrosion at 50°C after 60s etching.
Fe
Binding Energ\' (eV)

Figure 6-31 : Surface scan of Fe 2P312 spectrum and curve fitting for the sour corros ion
after 70 hours at 90°C after 60s etching.
107
45
40
7J5 130 i"5 no 11 5 710 105
B1I1dmg Ener gy (eV)
Figure 6-32: Surface scan of Fe 2P3/2 spectrum and curve fitting for the sour cOlTosion
after 70 hours at lSoe after 60s etching.
aj C3 . """,,I
Uncorroded
(as polished)
+ .....pJ ron Ca rbona te

• • • • • • •...................... • Ill'" C". bIU!l
b)
....... ~ r,.I<'l ten.'lt
G
Sweet pre-corrosion at 50 C
(After 2.5 hours)
Iron Sulphide
(Fi rst ayer) Iron Sulo de
Imn Sulnhi e
~. c) .... (FIrst Lay er)
(Sst.;(lIId La)"" I ~ " " " ~~ . _. ··..... Iror· Ca. oor·ate
I, or' Carb onate , . . ....•..
· · · · ~ lr()n Ca r :Jt e
Iron Ca rbide . . .. '
Sour corrosion at 90 C Sour corrosion at 15<.J C

(After 70 hours ) (After 70 hours )
Figure 6-33 : Summary of XPS results; a) UncolToded ; b) Sweet at sooe after 2.S
hours, c) Sour at 90 0 e after 70 hours, d) Sour at lS oe after 70 hours
108
The specimen at 90°C sour contains two layers of iron sulphide, howeyer for
specimens at 15°C only one layer of iron sulphide is detected. The presence of
dominant iron sulphide species at 90°C sour specimens explains the difference of 0.17
mm/yr corrosion rate observed between the high and low temperature sour
environments. This is supported by Pugh et aI., who showed that the corrosion rate
decreased with increasing temperature and claimed that a more protective FeS film
formed at high temperatures compared to lower temperatures [120].
6.7 Summary
This chapter revealed surface film characterisation for sweet pre-corrosion
specimens from 0.5 hours to 72 hours and sour specimens at different temperatures
using various surface analysis techniques. The studies reveal that the morphology of
sweet films is denser and more compact on the external part of the film and some
porous structures at the bottom of the film. Chemical analysis observed the presence
of mixed iron carbonate and iron carbide film under the test conditions, which means
the films are semi-protective. Under sour conditions, these studies reveal that iron
sulphide is the predominant product for 90°C specimens, which provides better
protection compared to 15°C specimens. The studies also show that both iron
carbonate and iron carbide are present in sour specimens.
109
Chapter 7: Investigation of pitting corrosion in sweet and sour

conditions
In this Chapter the mam objective is to understand pitting and pitting

inhibition. The corrosion films in sweet and sour conditions were evaluated
previously in Chapter 6. This chapter studies the findings from the previous chapter as
a reference to understand the film breakdown phenomena, which lead to pitting
growth. This chapter presents and discusses the natural pitting growth on X65 carbon
steel surface in sweet and sour conditions and the effect of inhibition in sweet
conditions. This chapter is divided into two stages; in the first stage, pitting growth
experiments have been performed at various times to understand the pitting depth
behaviour with respect to time. The second stage experiments use the first stage
results as a reference to evaluate the performance of phosphate ester and imidazoline
inhibitors towards pitting propagation. The corrosion rate was monitored by
electrochemical methods and profilometry analyses were used to determine the pit
depth.
7.1 Pitting growth

7.1.1 Corrosion current measurement for sweet experiments
The sweet experiments were performed in 850ml, 10% sodium chloride at 1
bar total pressure of carbon dioxide gas with the temperature controlled at 80°C. The
exposure time varied from 6 to 150 hours in different experiments. Electrochemical
corrosion measurements using DC linear polarisation were carried out to monitor the
corrosion rate during the 150 hour experiments. The film formation procedure was
developed, which was inspired primarily by the previously published protective scale
formation procedure by Han et al [55]. This film formation procedure, as described
below, was developed with reference to the film characterisation findings from
Chapter 6 to create a semi protective film that could lead to film breakdown. The
change in conditions was introduced in 2 hour steps to allow different film properties
to grow on the surface in different layers to promote the film breakdown and have
pitting. The corrosion rates after 2 hours immersed in the solution ranged between
2.75 mm/yr and 3.25 mm/yr. After 2 hours, the pH of the solution was initially around
pH 3.9, and then the pH was adjusted to 5.65 by adding sodium bicarbonate
(NaH C0 3). This decreased the corrosion rate significantly to within the range of 1.75
110
mmlyr to 2.25 mmlyr, as shown in Figure 7-1 . During thi s period more compact iron
carbonate film formed on top of the mixed iron carbonate and iron carbide film , as
shown in Figure 7-2.
3.5
I:' 3
~
E 2.5
5
....<l< 2 --
,..
~
C 1.5
0
'r;; ...... . /~ _ .1
,..0 l/ ~ V !\. T 1 I
0 ..- lIo..
1
T
-1 '1'1 "T ~ ~ ,..

T
++' r1_
T
U
0.5
[TTT T TJ "1'
~L .,j/,
L
.qr"I I
o 1
o 20 40 60 80 100 120 140
Time (hour)
Figure 7-1: Corrosion rate versu s time for the X65 carbon steel in C02 saturated , 10%
2
NaCI brine at 80°C, pH 5.65 and 1000ppm Fe +
4 hours
material
Figure 7-2 : SEM cross-section image of X65 carbon steel in CO 2 saturated lO% NaCl,
pH 5.65 at 80°C after 4 hours

11 1
After 4 hours, 1000ppm of iron chloride (FeC h) was added, which decreased
the corrosion rate to a range of 0.75 mm/yr, and thi s rem ained fairl y constant for up to
20 hours. The corrosion rate started to increase after 24 hours to aro und 1.25 mrnlyr
until 72 hours and then the corrosion rate dropped to 0.75 mrnlyr until the end of the
experiment at 150 hours. The corrosion rate obtained is supported by Han et al. who
observed that the corrosion rate at 0.3 supersaturation of FeC0 3 80°C and pH 5.6 was
0.75 mm/yr during the chemical scale removal process [55] . It is interestin g to
observe the pit growth from an in-situ camera observation in Figure 7- 3. The ca mera
displays the real time image and recorded the image every 20 seconds.
Figure 7- 3: In- situ camera observation on pit initiation on X65 carbon steel in CO:>.
2
saturated 10% NaCl , pH 5.65 , 1000ppm Fe +, at 80°C from 5 hours to 8 hours
112
The initiation of pits was observed after 5 hours at uncorroded spots and
propagated to 30llm in pit mouth diameter until 8 hours. The pit diameter grows
actively in the first 3 hours after initiation and then the pit diameter propagation rate
slow s down and stops at 10 hours, as shown in Figure 7-4.
e)100 h f)150 h
o
o
Figure 7-4: In-situ camera observation on film formation s at the pit site on X65
2
carbon steel in CO2 saturated 10% NaCl , pH 5.65 , 1000ppm Fe +, at 80°C from 10
hours to 150 hours
The uncorroded spots represented by the white regions around the pits could
indicate a lower pH area or a chloride cap. The in-situ image also shows that the
unc o lToded spots aro und the pit site remai ned during the pitting initiation proce ss :
howe ve r, the film fOllllation started taking place at the uncorroded site after the pitting
11 3
growth proce ss s low ed d own after 7 hours. T he ac ti ve fi 1m growth continue unti l SO

hours and then the film £To \,\l th doe s no t show m uch difference until I SO hours. Fi Q: ure
~ ~
7-5 sho w the SEM im age of iron carbonate fil m on the surface after IS O ho ur and
so me surface dam age appears in whi ch the fi lm le aves a footpri nt of iron carbonate
cry stals. Figure 7-6 show s the cross-secti onal image of the iron carbonate film. w hic h
filled the iro n carbide ne two rk left behind after 15 0 hours. Gul brandsen et a l. showed
that long time ex posure at 50°C , pH 5 in CO 2 conditi ons m ay re sult in a thi cker
ce m e ntite film Q:Towth on the surface and lead to hi Q:her ave raQ:e corros ion rate and
~ ~ ~
locali sed attac k [1 92 ]. Thi s show s that the pits propagate beneath the po rous corros ion
film and coalesce into a larger pit and the rem ainin g corro sion film on top will fill the
pit comple te ly or be re m oved ste pw ise by fl ow [62 . 55]. T he buil d u p and c hange of
kinetics of the iron carbonate film \'\l ith time cause s the varia ti o n of corros io n rate
durin g the ex perime nt s.
Fi gure 7-5: SEM surface im age on X65 carbon stee l in CO 2 saturated 10 Sle NaC l. pH
~ ~
5.65 , 1000ppm F e 2+. at 80°C aft er 150 hours
. .~
, .
\ ..
... ..... ". .
ma lerial
F igure 7-6 : SEM c ross-sec ti on on X65 c arb on steel in C02 saturated 10°c aCl. pH
2
5 .65 . 1000ppm Fe +. at O°C after ISO hours
11 4
7.1.2 Corrosion current measurement for sour experiments

Sour experiments were performed in 10% NaCl for 4 hours at 80°C at vari ous
conditions to explore the optimum condition to obtain deep pits again st a relati vel y
low corrosion rate . The first specimen , which was immersed in 10% NaCl and natural
pH at around 4 showed a consistent corrosion rate of 0.8 mm/yr for the duration of the
4-hour experiment. The second specimen, which was immersed wi th the addition of
sodium bicarbonate (NaHC0 3) to adjust the pH to 5.65, showed th at the cOlTosion rate
decreased significantly to 0.4 mm/yr. However, the third specimen with an adjusted
2
pH of 5.65 and 1000ppm Fe + showed contrasting beh aviour with an increased
corrosion rate of 16 mm/yr, as shown in Figure 7-7.
~
.....
>-.
E
E
18
16
14
/
.. -
'-' 12
Q)
10
/
'iil
..... 8
7
:::
0 6
/
------ -
VJ
0 4
-----
.....
U
0
2
0
'/ -..... - - - - -
o 0.5 1. 5 2 2.5 3 3. 5 4
Time (hour)
____ 10%NaCi ----.- 10%NaC I. pH 5.65 -+- 10o/cNaC I.pH 5.65 , 1000ppm Fe2+
Figure 7-7: Corrosion rate versus time for the X65 carbon steel in 10% H2S, 90% CO 2
saturated, 10% NaCl brine at 80°C
Therefore, based on the earlier test re sults , an extended te st was carried out at
10% NaC1 with pH 5.65 for 96 hours to study the behaviour of pitting propagation in
sour conditions. In the first 10 minutes of the test, the corrosion rate was aro und 0.7
mm/yr. The corrosion rate decreases to 0 .15 mm/yr after 4 hours as the protective iron
sulphide film is built up, as shown in Figure 7-8.
After 24 hours of immersion the corrosion rate starts to increase to 0.4 mm/yr
and fluctuate s between the range 0.3 mm/yr to 0.4 mm/yr until the end of the
ex periment at 96 hours. The corrosion rate obtai ned is supported by Svenningsen et
aI. , who observed that the corrosion rate at 60°C , pH 5 with a mixture of 50 9c H ~ S and
50% C02 was 0.3 mm/yr during 72 hours exposure [127] . After the 96 hour te st. the
115
SEM image shows th at an iron sulphide f ilm formed on the surface , as shown in
Figure 7-9. T he fil m layer con sists of two irregul ar layers of crys tal s in whi c h the top
layer was poorl y adherent to the surface and formed pi t clu sters [4, 130].
0.9
~ 0.8
~
I-
>-,
E 0.7
~
E 0.6
II)
0.5
~
l-
~
=----
e 0.4
0
.." 0.3 ~
0
-----
I-
0 0.2 i
U Y
0.1
o
o 10 20 30 40 50 60 70 80 90
T ime (hour)
Figure 7-8: Corrosion rate vers us time for the X65 carbon stee l in 10% H, S 90% CO ,
saturated , 10% NaCI brine at 80°C, pH 5.65 - , -
Figure 7-9: SEM im age on X65 carbon steel in 10 % H 2S, 90% CO 2 in 10% at 80°C
in sour afte r 96 hours
7.1.3 Pit Depth analysis for sweet experiments

The analyses were conducted using contact surface profilometry Tal ys urf-120
and non-contac t w hite light interfe rome ter WYCONT3300S . Pit growth va rie s in
numbe r and size on the surface but the maxi mum pi t depth is the main parameter th at
leads to fa ilure. Figure 7- 10 shown the pits obtained after 150 hours exposure time. A
2Dim age as show n in F igure 7-1 Ob showing that the deepe st pit s obtained are around
73 f.1 m . T he pit growth is scattered all over the surface a shown in Figure 7 -1 0 (a-f) .
116
b) X Profi le
."" ....
. , , urr
~ =
=
.,
?
c) Y Profi le
e)
I '
I
I
------------------~
x-
I
16 0TTl
Y = } ,m l
of ')
I ':" ~ rn
____..-J
Figure 7-10: Profilometry analysis for 150 hours specimens of X65 carbon in CO 2
2
saturated 10 % NaCI brine at 80°C, pH 5.65 , 1000ppm Fe + and I bar CO 2 ; a) 2D view
of pits surface , b) Cross-section for x-profile from 2D view , c) 3D View of pits
surface , d) Cross-section for y-profile from 2D view , e) 3D view of pits surface , f)
Cross-section from 3D view pits
The depth varies from micro pits, starting at I f.l m to the deepest pit at around
73f.lm . In thi s stud y, the e ntire surface of the sample was analysed with the threshold
set acco rding to the va lue of the third deepes t pit on the sUlface to determine the three
dee pest pit depths on the surface. These three maximum pits obtained o n the urface
were eva lu ated to measure the ex tent of pitting cOlTos io n. beca use the deepe st pit is
117
the main parameter that can cause failure . Figure 7-11 shows the max imum pit depth
and average of three maximum pit depth s obtained on the surface at different time s.
Te sts were conducted for duration s of 6, 24, 70 , 96 , 120 and 150 hours in separate
experiments to obtain the pit depth , which is necessary for inhibitor evaluation.
80
70
.----, 60
E
-3 50
..c 40
0.
(\)
a..... 30
0... 20
10
0
0 10 20 30 40 50 60 70 80 90 100 11 0 120 130 140 150
Time (hours)
-+- Max. Pit Depth ..... Ave Pit Dep th

Figure 7-11: Maximum pit depth and average of 3 maximum pit depth of X65 carbon
2
in CO 2 saturated 10% NaCl brine at 80°C , pH 5.65 , 1000ppm Fe + and I bar total
pressure at different times
The results show that the pit depth increases over time, which means that the
longer tests generate more severe localised corrosion and, thu s, deeper pits as
expected. Pitting depths obtained for the 6 hours test are around 15f..1m . However, the
pitting depth obtained for 24 and 70 hours was around 12f..1 m. No increase in the depth
over time is shown for the 24 hours and 70 hours specimen s. However, the tests at 96 ,
120 and 150 hours show a significant increase in pitting depth over time with a linear
propagation rate.
The results show that the pitting propagation was non-linear in the fir st 72
hours due to the film build-up process overtime, as indicated by the fluctuation in the
corrosion rate from 20 hours to 70 hours in Figure 7-1 . After 72 hours, a stab le film
form is shown by the consistent corrosion rate , whi ch enhance s the propagati on
proc ess.
11 8
7.1.4 Pit depth analysis of sour experiments

The pitting that was generated from all 4-hour tests did not show a signi ficant
final pit depth to enable any difference between the condition s to be determined.
Figure 7-12 show s that the average pits generated are around 6/Jm to 8/Jm depth for
all 4-hour tests and for the extended test to 96 hours, the pit depth obtained is around
30/J m depth . Figure 7 -13b and Figure 7 - 13d shows that the profilometry anal ys is for
the pits obtained from the 4-hours test to have a depth of 8.9/Jm and after 96 hours
was 31.4 /J m . Figure 7-13a shows that the pit grows as a single pit on the surface but
the surrounding area is not effected by pitting cOITosion. After 96 hours, Figure 7 - 13e
show s that single pits are merged together to form bi gger pits with greater depth. T hi s
also shows that the pit depth increases over time and generates more severe localized
corrosion and deeper pits.
35 ,
3U
::!5
E 2U
.2;
..<:
0..
<L)
0 15
~
0-
IU
U
10'70 N aCL 4h 10'« ' aCI. pH5.65 . .Jh 10'« Na CL pHS .65 . 96h
10'70 aCi. pH5 .65 . Fc2+. 4h
Condition s
Figure 7-12: Pit Depth of X65 carbon in 10% H 2S, 90% CO 2 saturated, 10% NaCI
brine at 80°C
119
a) b)
X Profi le
1\ 1'32 um
~
.... '<7
"'-·I.-'"\fV'V~ ~ V · ".t,..---'"'( '~J~-V\

\, '"'" '"'"
Ce:.,"-
c .. . . 'T I
, .: ~ ? urn
1
--
- ~ .: .J 1""1
----~
..
d)
- - A
'<7
X Profil e
..l: urn
~
....
rr ~~l~~
,
_ Ir-~~t}/
' ./
/
. C' ~H J £
I n
1 urn
" C' :~ c,um )

-_'9.url _
.. t--
e) f) Y Profile
, 108 um
.,
Figure 7-13 : Profilometer anal ysis of X65 carbon steel In 10% H 2S, 90% CO 2
saturated, 10% NaCl brine at 80°C, pH 5.65 ; a) 2D view of pits surface after 4 hours,
b) Cross-section from 2D view pits after 4 hours, c) 2D view of pits surface after 96
hours , d) Cross-section for x-profile from 2D view, e) 3D view of pits surface after 96
hours, f) Cross-section for y-profile from 2D view
120
7.2 Inhibition of pitting in sweet experiment

7.2.1 Corrosion current measurement for phosphate ester inhibitor
Corrosion rates were monitored durin g the ex periment to observe the change
aft er different concentrations of pho sphate ester were added into the test vesse l after
120 hours pre-corrosion. The effectivene ss of the inhibitor was evaluated towards
overall corro sion protection in which the main goal is preventing the pitting
propagation, and, at the same time , to control the general corrosion. Figure 7-1 4
show s the corro sion rate observed during the te st.
4.s ~-----------------------------------------r--------.--------
4+-----------------------------------------~
Inhibit or
~ added
~ 3.s ~----------------------------------------~
E 3 ~~=~----~-----~-
E
'---'
(J) 2.5 _ f---------------------------------------------
....ro
~ 2 ~~--------~--------------------------------~
-=:
o I. s~~~~~~~~~~~!:~~~~~~~~~~~~~~~~~~l
.§ It
U 0.5
O ~~~~~~----~--~~--~~--~~====~~
o 20 40 60 80 100 120 140
Time (hour)
___ 10ppm -+- 2s ppm ___ sOp pm ......... 7sppm ---- 100ppm ........ 200ppm --- 300ppm -+- Blank
Figure 7-14: Corrosion rate versus time for the X65 carbon stee l in CO 2 saturated,
2
10% NaCI brine at 80°C , pH 5.65 and 1000ppm Fe + with different concentrati ons of
phosphate ester
The corrosion rate at 120 hours pre-corrosion was observed and varies in the
range between 0 .3 mmlyr and 1.3 mm/yr. The corro sion rate variation could not be
avoided with such a long pre-corro sion time due to the form ati on of a cementite laye r
on the surface mi xed with iron carbonate film to offer a semi-protecti ve film in this
test condition [91 , 192]. Wong et al. also observed that the corrosion rate varies
between 0.25 mm/yr and 1 mm/yr after 15 hours corrosion at 10000ppm cr, pH 6.5 ,
80°C with saturated CO 2 [99]. Thi s is supported by Han et al. who showed that at pH
5.65 , the solubility of iro n carbonate is at the saturati on line and sugge sted that
locali sed co rrosion is more likely to propagate [50]. Han et al. also showed that at
121
10% NaC l, the solubility of FeC0 3 increases, which makes it more diffi c ult to form a
fully protec ti ve FeC0 3 film and increases localised attack [50] . The corrosion rate
effect fo r every inhibitor concentrati on was compared individuall y before the in hibitor
was added and after the inhibitor was added at 120 hours. Figure 7-15 shows the
expanded version of the corrosion rate with time from 110 hours to 150 hours .
3.5
Inhibitor added 2S ppm

~
.....
--
>.
E
E
2.5
2
~ SOppm
e<:l
..... 300ppm
c 1. 5
0
Vl
IOppm
0
.....
0 IOOppm
U Blank
0.5
200ppm
0 7Sppm
11 0 11 5 120 125 130 135 1.. 0 145 150
Ti me (hour)
........... 10ppm -+- 2S ppm ___ SOppm ....... 7Sppm ........ IOOppm -+- 200pp m ........... 300ppm -+- Bl ank
Figure 7-15 : Expanded version of corrosion rate ve rsus time fo r the X65 carbon stee l
2
in CO 2 saturated , 10% NaCl brine at 80°C , pH 5. 65 and 1000ppm Fe + wi th di ffe rent
concentrations of phosphate ester
The corro sion rate measured for 10ppm, 25ppm and 50ppm inhi bitors shows a
50% inc rease in the corros ion rate after the inhibitor was added . The general corrosion
rate almost doubles at lower concentrations. The corrosion rate , which was mo nitored
for 75ppm, 100ppm, 200ppm and 300ppm inhibitor, did not show any significant
change in the corrosion rate after the inhibitor was added. This res ul t is supported by
Foss et al ., w ho showed that there was no further effect on the corros ion rate when the
phosphate ester inhibitor was added after 280 hours pre-corros ion at 60°C, 0.8bar CO 2
[9 1] . However, W ong et a!. showed that phosphate es ter reduces the corrosion rate
significantl y when added at the beginning of the test [98]. Thi s is supported by
Gulbrandsen e t a!. , who showed th at a long pre-corrosion ti me at 50°C, pH 5 in CO 2
conditi ons may im pa ir inhi bitor pelform ance due to the presence of a laye r of
ce me ntite on the sUIface , which makes the surface un stable due to the large ca thod ic
surface [ 192]. T hi s shows that at the above minim um effective conce ntrati on of
122
inhibitor, the phosphate ester does not show a significant effect on the corrosion rate
due to the pre-corrosion film that had already built up in the first 120 hours. The pre-
corrosion films have a strong influence in controlling the corrosion rate and
kinetically hinder the corrosion force [192]. The pre-corrosion conditions simulate the
situation to inhibit a pipeline that is already in service, in which the surface might be
covered with iron carbonate precipitates, uncorodded iron carbide and many different
types of scale [192].
7.2.2 Corrosion current measurement for imidazoline inhibitors

Imidazoline inhibitors were also evaluated using the same procedure as the
phosphate ester inhibitor for which the main goal is to prevent the pitting propagation
and at the same time to control the general corrosion. The performance of imidazoline
inhibitors is better in terms of controlling the corrosion rate, mainly at higher
concentrations, as shown in Figure 7-16. Figure 7-17 shows the expanded version of
the corrosion rate with times from 110 hours to 150 hours. The corrosion rate
measured for the lOppm inhibitor initially shows a 25% increase after the inhibitor
was added to the test vessels, however, it improved the performance with time
towards the end of the test. There were no significant changes in the monitored
corrosion rates for 25ppm, 50ppm, 75ppm and 100ppm inhibitors.
After the concentration of the inhibitor was increased to 200ppm and 300ppm,
a 50% decrease in the corrosion rate was observed. These results are supported by
Foss et al., who showed a decrease in the corrosion rate when imidazoline inhibitor
was added after 290 hours pre-corrosion at 60°C, 0.8bar CO 2 [91]. Wong et al. also
showed that imidazoline reduces the corrosion rate significantly when added at the
beginning of the test [98]. This shows that at above the minimum concentrations of
imidazoline, the inhibitor will influence the existing corrosion film on the surface to
reduce the corrosion rate. Chokshi et al. observed that imidazoline inhibitors could
decrease the concentration of Fe 2+ at the pre-corrosion surface and hamper the growth
of FeC0 3 to slow down the anodic as well as the cathodic reactions [65].
123
~
..... 3.5 Inhibitor
>-.
added
E 3
E
'-" 2.5
Il.)
~ 2
.....
c 15
0
:/J
0
.....
0
U 0.5
0
0 20 40 60 80 100 120 1-10
Time (hour)
..... Blank ---...- 10ppm -+- 25 ppm ~ 50ppm -+- 75pp m -+- 100ppm -+- 200ppm -+- 300ppm
Figure 7-16: Corrosion rate versus time for the X65 carbon steel in CO 2 saturated,
10% NaCl brine at 80°C, pH 5.65 and 1000ppm Fe 2+ with different concentrations of
imidazoline
18
1.6
Inhibitor added
----. 14
I-
>-.
E 12
E-
ll.)
.....
ro
l- 0.8 lank
e
0 5ppm
0.6
:Il
0 OOppm
I-
0 04
50ppm
U 75 ppm
0.2 OOppm
200ppm
0
11 0 11 5 120 125 130 135 1.:10 145 150
Time (hour)
......... Blank - . - 10ppm -+- 25 ppm -+- 50p pm ~ 7 5 ppm -+- IOOppm ~ 200ppm -+- 300 ppm
Figure 7- 17: Expanded version of corrosion rate versus time for the X65 carbon steel
2
in CO 2 saturated, 10% NaCl brine at 80°C , pH 5.65 and 1000ppm Fe + with different
concentrations of imjdazoline
124
7.2.3 Pit depth analysis for phosphate ester inhibitor

For the blank test, the results show that, on average , the pit depth ranged
between 20l1m and 4811m after 120 hours and between 40l1m and 7311m after 150
hours . Phosphate ester was introduced at various concentrations to the experiment at
120 hours to control pitting propagation between 120 hours and 150 hours. Figure 7-
18 shows that phosphate ester can control the pit propagation if a suffici ent
concentration is applied.
80
70
60 \
---E 50
· -i~\
:::l...
'-'
..s:: 40
J\ .A
•
0.
<l.)
Cl 30 \
......
0: 20
~ ~
• ~
~----:!.
10
0
o 25 50 75 100 125 150 175 200 225 250 275 300
Inhibitor concentration (ppm )
...... Ma x. Pit Depth -:~ Ave Pit Depth
Figure 7- 18: Maximum pit depth and average of 3 maximum pit depth of X65 carbon
2
in CO 2 saturated 10% NaCI brine at 80°C, pH 5.65, 1000ppm Fe + with different
concentrations of phosphate ester
Phosphate ester pelforms at effective performance at concentrations between

2Sppm to 200ppm with the final pit depth obtained between 17 11m and 27 11 111 .
Figure 7-19 (a-d) shows that the pit depth profile at 100ppm phosphate ester with the
pit depth obtained around 2711m. At 300ppm, the phosphate ester inhibitor has little
effect on slowing down the pit propagation, in which the final pit depth obtained was
between 37 11m and 41 11m ; the decrease in the inhibition efficiency is postul ated to be
due to the higher inhibitor concentration beyond the critical concentration valu e of the
inhibitor. However, with a low concentration of 10ppm phosphate ester, the pitting
propagation was not decreased , obtaining a final pit depth of around 4611 m to 6311 m.
as shown in Figure 7- 19.

125
a) b)
X Profi le
: )um
c) d)
Y Profile
, 1 7:- urn
Figure 7- 19: Profilometer analysis of X65 carbon steel in CO 2 saturated 10% NaCI
2
brine at 80°C, pH 5.65 , 1000ppm Fe + with different concentrations of phosphate
ester; a) 2D view of pits surface at 100ppm, b) Cross-section from 2D view pit s at
100ppm, c) 3D view of pits surface at 100ppm, d) Cross-sec tion for x-profile from 20
view at 100ppm, e) 2D view of pits surface at 10ppm, f) Cross-sec ti on for y-profil e
from 2D view at 10ppm
The lack of any signific ant difference from the bl ank test is po stul ated to be
due to the insuffici ent effect of the inhibitor, which reduced the inhibitor performa nce.
It is interesting to co mpare the correlation between the corrosion rate effect and the
final pit de pth obtained, as at 10ppm phosph ate ester both the corros ion rate and pit
depth result show a decrease in perfonnance.
126
7.2.4 Pit depth analysis for imidazoline inhibitors

Imidazoline slows down the pitting propagati on at almos t all concentrati ons
between 10ppm and 300ppm , as shown in Figure 7-20.
80
70
---. 60
E
=- 50
_...
'--'
..c
0..
I])
0
~
0:
40
30
20
-1
\.
~.:.-r
... .,..- .
.i
10
0
o 25 50 75 100 125 150 175 200 22 5 250 275 300
Inhibito r conce ntratio n (ppm )

~ Max. Pit Depth - · - Ave Pit Depth
Figure 7-20 : Maximum pit depth and average of 3 max imum pit depth of X65 carbon
in CO 2 saturated 10% NaCI brine at 80°C , pH 5.65 , 1000ppm Fe 2+ with different
concentrations of imidazoline
Imidazoline perform s at effective concentrati on between 25ppm and 300ppm

where the maximum pit depth obtained was between 17.3 /Jm and 20 .5 /Jm . Figure 7-
2 1(a-d) shows that at 100ppm the pit depth obtain was 30.4/Jm and the 2D and 3D
im age show s that the pit di stribution on the surface we re in the fo rm of single pits
with less general corrosion attacked . Imidazoline has little effect on slow ing down
the pit propagation at 10ppm where the maximum pit depth obtained was 34 .4 /J m ,
whi c h was postulated to be due to the insufficie nt effec t of the inhibitor, whi ch
reduced the inhibitor performance. Imidazoline also has little effec t on slowing down
the pit propagati on at 300ppm where the maximum pit depth obtained was 36.4 /J m ,
as show n in Figure 7-2 1f, whic h was postul ated to be due to the hi gher inhibitor
concentrati on beyond the inhibitor concentrati on critical va lue.
Imidazo line show s a good perfo rmance in alm ost all conce ntrations tested
toward s ge neral corrosion and pittin g. It is interesting to com pare the mec hani sm of
127
action betwee n imidazoline and phosphate ester toward s cOlTos ion rate and pit depth
in di sc ussion chapter.
a) b)
X Profi le
'. : 1 um
c) d) Y Profi le
."
f) X Profi le
\ 209 urn
( ')
'<7 ...
.
5
c
3
----- - ---- ---
Figure 7-21: Profilometer analysis of X65 carbon steel in CO 2 saturated 10% NaCl
brine at 80°C, pH 5.65, 1000ppm Fe 2+ with different concentrations of imidazoline ; a)
2D view of pits surface at 100ppm, b) Cross-section from 20 view pits at 100ppm, c)
3D view of pits surface at 100ppm, d) Cross-section for x-profile from 20 view at
100ppm, e) 2D view of pits surface at 300ppm, f) Cross-section for x-profi le from 2D
view at 300ppm
128
7.3 Summary
This chapter revealed the pitting growth process from 6 hours to 150 hours.
The study reveals that the pit does not show a consistent pit depth increase over time
until 70 hours of immersing time. However, tests at 96, 120 and 150 hours show a
linear increase of pitting depth over time. Both phosphate ester and imidazoline
inhibitors showed excellent performance to stop pit propagation if optimum
concentrations are applied. However, imidazoline shows a better performance in
reducing the general corrosion rate compared to phosphate ester.
129
Chapter 8: Evaluation of inhibitor performance using artificial pit

technique under sweet conditions
In the previous chapter, results from the characterisation of the corrosion film
under sweet and sour conditions, natural pitting growth and inhibition effects on
natural pitting were presented. In order to accelerate the inhibition test method and
further understand the pitting interaction between the inhibitors and corrosion films,
an in-situ monitoring technique was developed and artificial pits were introduced to
the studies. This chapter uses the pitting inhibition test procedure from Chapter 7 as a
reference and develops an accelerated inhibition test procedure with in-situ
monitoring technique and artificial pits in sweet conditions. The artificial pit growth
on X65 carbon steel surfaces in sweet conditions was assessed using an in-situ
monitoring technique. Phosphate ester and imidazoline inhibitors were used. The
inhibitors were evaluated in terms of artificial pit propagation and using DC linear
polarisation resistance (LPR) test methodologies. Assessment of the pits by FfIR
analysis was used to characterise the chemical constituents of the surface and
profilometer analysis was used to determine the pit depths.

Electrochemical corrosion measurements usmg DC linear polarisation
resistance tests were carried out to monitor the corrosion rate after every step until a
protective film was obtained in the first 3.5 hours. The corrosion rates after 1 hour
immersed in the solution were 2.5 mmlyr. After 1.5 hours, the pH was adjusted to
5.65 by adding sodium bicarbonate (NaHC0 3), which decreased the corrosion rate
significantly to 1.75, as shown in Figure 8-1. After 3 hours, lOOOppm ofiron chloride
(FeCI 2 ) was added, which dropped the corrosion rate to 1.25 mmlyr. After 4 hours,
electrochemical corrosion measurements using a potentiostatic test were carried out.
The potentiostatic test procedure was developed, which was primarily inspired and
previously published by Neville et aI., involving scanning stainless steel to 100mV
more positive then SCE and holding it constant for a period of time to observe the
localised effects [58]. During the test development stage, the constant electrode
potential applied was varied to obtain pits of the required depth. A constant electrode
potential at 100m V more positive than the free corrosion potential was chosen in this
test to activate the artificial pit on the surface to a desired pit depth.
130
\ pH adjusted to 5.65 \1 OOOppm FeCI,- added

~
....
E 2.5
3
1 I
-
E 1 ~
--- ----+
Q)
ro.... 2
-----
~
e: T
0 1.5
'iii
0
....
0
()
0.5
05 1.5 2 2.5 3 3.5 4
Time (hour)
Figure 8-1: Corrosion rate versus time for the first 3.5 hours for the step change
process on X65 carbon steel in CO 2 saturated, 10% NaCI brine at 80°C, pH 5.65 and
1000ppm Fe 2+
Figure 8-2 presents the potentiostatic results for three experiments without
inhibitor. It shows that, initially, the current decreased in the first 100s and is
maintained in the range between 4mA to 7mA for the next 35000s (9.5 hours) for all 3
runs. After that, Run 2 shows that the current keeps constant until the end of the 24-
hour test but Run 1 shows that the current increased to 8mA and finished at 7mA.
However, Run 3 shows that the current decreased to 2mA and finished at 3mA. The
results showed significant current variation between the 3 runs after 9.5 hours, which
could be due to the long time exposure, and indicated the formation of a layer of
cementite on the surface mixed with a film of iron carbonate and the growth and
propagation of pits on the surface [91, 192, 193].
The current represents the general dissolution behaviour of the surface, which
IS influenced by the film breakdown process of the corrosion film. Mok et al.
observed that potential fluctuation in a long-term test indicates the pit propagation
process characteristic [193]. Iimura et al. also observed that the change in current
could be attributed to the change of surface condition of the pit and/or the change of
property of the formed corrosion products covering the pit [194]. This is also
supported by Cheng et al. who observed that the current fluctuation was caused by the
pit growth kinetics, which are associated with a new deposited cover over the mouth
of the pit [195]. Depending on the test conditions, the deposit present on the pit could
contain flaws or defects from ionic current passed between the pit anolyte and the
bulk solution [195]. Referring to Figure 7.1 the corrosion rate obser\'ed in this
condition is around 0.75 mmfyr with the formation of a layer of cementite on the
13 1
surface mi xed with iron carbonate film to offer a semi -protecti ve film . The current
behaviour in thi s test show s a simil ar fl uctuation charac teri stic with the linear
polarization behavio ur for the 150 hours bl ank test in Chapter 7 and shows a good
correlati on in simul atin g the test conditi ons in a shorter ti me.
0.0 1
0.008
~ 0.006
c:
II)
t 0.004
=:
U
0.002
0
10 100 1000 10000
Time (S)
-+- Run 1 ---- Run 2 --..- Run 3
Figure 8-2: Potentiostatic polari sation curve at 4 hours to 24 hours on X65 carbon
2
steel in CO 2 saturated 10% NaCI brine at 80°C , pH 5.65 and 1000ppm Fe + wi thout
inhibitor
8.1.1 Effect of phosphate ester

The pe rform ance of phosphate ester inhibitor was studied by adding di ffere nt
concentrati ons after 3.5 hours. Fi gure 8-3 presents the results of the potentiostatic
tests with different concentrati ons of phosphate ester. The presence of inhibitors does
not significantly dec rease the c urrent but causes current oscillations postul ated to be
due to the reacti on of the inhibitor on the surface. It shows that th e lowe st
concentrati on of inhibitor results in hi gher CUITents up to 8mA. However when the
inhibitor concentrati on increases, it does not show much effect on the overall tre nd
compared to the tests without inhibitor.
Figure 8-4 presents the final current effects on inhibitor concentrations. It

shows that the final current at 25 ppm inhibitors is higher than the test without
inhibitor, however, when the inhibitor concentrati on increases to 50ppm , the fin al
current is lower than the test without inhibitor. It is interesting to observe th at at
100ppm and 200ppm, there is no signific ant change in the fin al current. Alink et al.
2
observed that phosphate ester type inhibitors fo rm fairly in so luble Fe + compl exe s and
132
are closely related to mInImUm effective concentration [106] . Thi s shows th at

phosphate ester inhibitor does not affect the current after it reache s the minimum
effect concentration , which under the conditions studied is 100ppm.
0.01
0.008
~ 0.006 + - -- - -----::;:::"....a:::::It:::II:::II::III..._ _~~__..___::::_____:_:_~____tI
:::
~ 0.004 1--/~-----:::~-::=~~~;t\;tif_~5;i::!
::I
u 0.002 +-----II'~~::=::::::::::!:::=::::~.....l.~:::..:~~~~tU
o +---------~----------~--------~~--------~------~
10 100 1000 10000
Time (s)
--- Blank - - 2S ppm - SOppm ~ 100ppm --k- 200pp m
Figure 8-3: Potentiostatic polarisation curve for 24-hour test on X65 carbon steel in
1
CO 2 saturated 10% NaCI brine at 80°C, pH 5.65 , 1000ppm Fe + and I bar total
pressure with different concentrations of phosphate ester
8.0
~ .
7.0
-----
@ 6.0
'-'
......
cQ) 5.0
I-;
I-;
::l 4.0
.- .. ------------------- ..
~
U
c
i.E
3.0
2.0
'. - . -
-
1.0
0.0
0 20 40 60 80 100 120 140 160 180 200
Inhibitor concentration (ppm)
Figure 8-4: Final potentiostatic current after 24-hour te st on X65 carbon steel in CO 2
2
saturated 10% NaCI brine at 80°C , pH 5.65 , 1000ppm Fe + and 1 bar total pres sure
with different concentrations of pho sphate ester

133
8.1.2 Effect of imidazoline

The performance of the imidazoline inhibitor was also studied. Figure 8-5
presents results of the potentiostatic tests when different concentrations of imidazoline
were added to the solution after 3.5 hours. The pre sence of inhibitors significantly
decreases the current. It shows that at 25ppm the current was 3mA ; as the inhibi tor
concentration increased to 200ppm it reduced the current down to less then 0.1rn A.
Figure 8-6 pre sents the final current effects on inhibitor concentrati ons.
0.007
0.006
0.005
""""'
:$ 0.004
C
Q)
t:: 0.00 3
:::l
U 0.002
0.001
0
10 100 lime (5) 1000 10000
--- Blank ~ 2Sppm --.- SO ppm --- 100ppm ---- 200 ppm
Figure 8-5: Potentiostatic polari sation curve for 24-hour test on X65 carbon steel in
2
CO 2 saturated 10% NaCI brine at 80°C, pH 5.65 , 1000ppm Fe + and 1 bar total
pre ssure with different concentrations of imidazoline
8
,-.,
<r:
s
'-"
.......
c
<l) H
T ,..,. - ......
t:
:=
::I
U
'@
c
"a- "" '-
t.r:
" " ...... -. --- - -- - "
0 -------
o 20 40 60 80 100 120 140 160 180 200
Inhibitor concentrati on (ppm)
Fi gure 8-6: Final potenti ostatic current after 24-hour test on X65 carbon steel in CO 2
2
saturated 10% NaCI brine at 80°C , pH 5.65 , 1000ppm Fe + and 1 bar total pressure
with di ffere nt concentrati ons of imidazoline
134
It shows that the final current for all concentrations is lower than the test
without inhibitor. This shows that imidazoline provides better protection to reduce the
current, which might be because the inhibitor protects the overall surface by providing
a barrier film [104].
8.2 In-situ camera monitoring techniques.

Surface images were recorded using a LABVIEW program. The program
displays the real time image and records the image every 20 seconds. Figure 8-7
shows an early stage image after the specimen was immersed into the solution. It
clearly shows that the film formation took place over the initial grinding lines on the
metal surface. This indicates that a vast amount of corrosion occurred on the surface
eradicating these marks on the surface in the first 20 minutes of the process. After that
the surface darkens due to the uniform formation of a film building up on the surface.
Areas of the surface continued to darken and the thicker film affects the ability to
focus the camera.
Figure 8-8 shows an image after increasing the light supply and refocusing the
surface. It shows that the film grows on the film and covers most of the surface with
some uncorroded areas still existing after 1 hour. After 1.5 hours, the pH was adjusted
to 5.65 by adding sodium bicarbonate (NaHC03) and the film continued to generate
uniformly to cover the overall surface, which caused a reduction in the corrosion rate.
After 3 hours, 1000ppm of iron chloride (FeCb) was added to achieve a high
concentration of Fe 2+, which generated a small black deposit on the surface. After 3.5
hours, the dissolved iron chloride formed a protective iron carbonate film on top of
the previous film and the film became richer and significantly decreased the corrosion
rate up to 24 hours. No significant growth in pit diameter was observed during the test
due to the geometry of the artificial pits, which have a large diameter pit mouth
compared to depth. It is likely that the corrosion product constitutes the edge of the pit
mouth covering the cementite layer left behind and the pit propagated beneath the
original corrosion film on top of the edge of the pit mouth [47, 194, 195]. This is
supported by Iimura et aI., who observed that pits were covered with corrosion
product and the pH within the pit dropped to 3.3 from 8.9 [194]. Nyborg shows that
based on video observation, the mesa corrosion attack grew beneath the original
135
corrosion film on top of the specimen 's surface leavin ba on ly a thin lid of ori 0ainal
corrosion film behind [47] .
Figure 8-7: In- situ image of X65 carbon steel up to 30 minutes in CO 2 saturated 10%
NaCI brine at 80°C without inhibitor; a) 1 min , b) 10 min , c) 20 min , d) 30 min .
,
.......
Figure 8-8: In- situ im age of X65 carbon steel in CO 2 saturated 10% NaC I brine at
80°C , pH 5.65 , 1000ppm Fe 2+ and 1 bar total pressure with out inhibitor; a) 0 .1 h, b) 1
h, c) 2 h, d) 3 h, e) 4 h, f) 5 h.
136

The in-situ camera was able to monitor the fi lm growth and the physical
interaction of the inhibitor with the film at the pit site . Figure 8-9 show s the effect of
pho sphate ester when it is present at different concentrati ons on the surface . At lower
inhibitor concentrations, it is seen that it promotes the form ati on of bl ack depos its on
the surface . After 24 hours, the specimen with 25ppm inhibitor was full y covered by
the black deposit, which creates a favourable conditi on for the pitting process .
However, after the inhibitor concentrations were increased to 50ppm, the formation of
the black deposit was reduced by a significant am ount. At 100ppm of inhibitor, the
black depo sit was seen to be at a minimum level compared to the other spec imens.
The black deposit is postulated to be a product from the reac ti on of the

phosphate ester and iron ions if the stochiometric ratio of the reac tion is not at the
2
effective concentration. Alik et al. observed that at a stochiometric rati o of Fe + to
phosphate ester, the product will provide effective protecti on [106]. The ph osphate
ester inhibitor has a limited solubility in brine and thi s affects the stabili sing
phosphate ester to complexes iron ion in the solution [106] . At 200ppm , it seems that
the black deposit starts to reform on the surface due to exceeding the optimum value
that is needed to protect the pit.
Fi gure 8-9: In- situ image of X65 carbon steel in C02 saturated 10 % NaC I brine at
80°C , pH 5.65 , 1000ppm Fe 2 + and 1 bar total pressure wi th phosphate ester; a) Blank
I , b) Blank 2 , c) 200ppm , d) 100ppm , e ) 50pp m, f) 25ppm .
137

Fi gure 8-10 shows the effec t of imidazoline when it is prese nt at different
concentrations on the surface. The interac tion betwee n the imidazo li ne and iron ion
creates a thicker film spread across the surface. At lower 200ppm inh ibitor
concentrations, it is seen that it prom otes the form ati on of a blac k deposi t on the
surface and enhance s the favourable pitting conditi on. However, after the inhibitor
concentrations were decreased to 100ppm, 50ppm and 25ppm, the form ation of the
black deposit is significantly reduced. At 100ppm of inhibitor, the black deposit is
seen to be at the minimum level compared to other specimens. lmidazoline has a good
solubility in brine resulting in the formation of an adsorbed surfac tant monolayer or
bilayer on the surface of the metal [98 ,104] . The black deposit is postul ated to be a
mixture product between the inhibitor film and the corrosion product film .
Figure 8-10: In- situ image of X65 carbon steel in CO 2 saturated 10% NaCI brine at
80°C , pH 5.65 , 1000ppm Fe 2+ and 1 bar total pre ssure with imidazoline; a) Bl ank 1, b)
Blank 2, c) 200ppm , d ) 100ppm, e) SOppm, f) 2Sppm .
8.3 Pit depth analysis

The analyses we re conducted using contac t surface profil ometry Talys urf-1 20
and non-cont ac t white li ght interferometer WYCO NT 3300S. T he arti ficial pits
ge nerated by a mi crohardness indenter to make the pit 9 /lm deep. T he blank te st was
cani ed out to assess the severity of the test condi tion and to e nable evaluati on of the
perfo rmance of the inhi bitor. Figure 8- 11 shows th e compari so n in pit depth res ults
138
between the artificial pit (AP) and natural pit (NP) on the surface of all three run s of
the blank test.
80
70
60
--
~
50
-
- -<
::::l...
'1.J
40
Q
0::: 30
20
10
0
.-\1hfiCl<11 PIt NJtll1 ;)l PIt
Figure 8-11 : Average of maximum pit depth of X65 carbon steel in CO:>. saturated
10% NaCI brine at 80°C, pH 5.65 , 1000ppm Fe 2+ and 1 bar total pressure with out
inhibitor
After the blank test was conducted for 24 hours the pit growth scattered all
over the surface, as shown in Figure 8-12 (a-f) ; the depth varied from micro pits to the
deepest pit at 10311m. The artificial pits on the surface propagated to around 48.911m
to 53 .111m deep , as shown in the 3D profilometer im age in Figure 8-12c and Figure 8-
12f. The artificial pit propagated both laterally and in the depth direction. It is very
interesting to compare the artificial pit image in Figure 8-12c and Figure 8-1 2f, and
the in -situ image of artificial pits in Figure 8.8f, which proves that the pit propagated
laterally but beneath the original corrosion film on top of the edge of the pit mouth.
Thi s is supported by Nyborg, who showed that the video observation revealed that the
original corrosion film covering the mesa attac k beneath the film could be broken off
by the mec hanic al forces caused by turbulent flow [47].
139
a) b)
0' =:
0 " mm
00
"CO
0,
(ii 'J
,~
"
1 ] !i )0
2Q
t':~ '0
c) d)
, "'-
-j,
_m
e) f)
00
5-~
0 50
o :.''} ~
O~
o i 5- ~
Q
X> ~-=
, :.'~
~ "
, ~
,,, 20
1~
'0
'"
Figure 8- 12: Artificial Pit Depth of X65 carbon stee l in CO 2 saturated 10% NaC I
2
brine at 80°C , pH 5.65 , 1000ppm Fe + and 1 bar total pressure after test without
inhibitors; a) 2D view of pits surfac e, b) 3D view of pits surface, c) 3D View of
artifi cial pits surface , d) 3D view of natural pits surface , e) 2D view of pits surface , f)
3D view of artificial pits surface.
W hile the potenti al applied also initiated and propagated other natural pi tting
on the sUITounding surface. The natural pits on the surface propaga ted to aro und an
average depth of 70l-lm , however, in some bl ank specimens the natural pit propagated
to 103 1-1 m as show s in Fi gure 8- 12d . The nature of the pi tting proce ss cau sed the
natural pit dep th to vary tremendously.
140

Phosphate ester was introduced to the experiment, which can control the
pitting propagation if the required concentration is applied . Figure 8- 13 shows the
comparison in pit depth results for the artificial and natural pits on the surface with
different concentrations of phosphate ester. At 200ppm of phosphate ester it slowed
the pitting propagation process down to 23 .5I1m , as shown in Figure 8-14(a-d).
120
100
E
80 .......
:::l.. 60
~ "-
, "
. ...
..c ,
a. ~
<li
o
0...
40
~ - ......... _- -- --------
20
o
o 20 40 60 80 100 120 140 160 180 200
Inh ibit or Con cen trat ions (ppm)
-+- MJ X Arlificl;)1 Pit - ... - Ave Artifl clJ I Pit MJX NJtu rJ I Pit s - . . - Ave NJ tu rJI Pit
Figure 8-13: Pit Depth ofX65 carbon steel in CO 2 saturated 10% NaCI brine at 80°C,
2
pH 5.65 , 1000ppm Fe + and 1 bar total pressure with phosphate ester.
However, with 25ppm of phosphate ester, the artificial pit propagated to

83.7I1m, which is significantly higher than the blank te st as shown in Figure 8-14f.
This is postulated to be because of the reduced adsorption of the inhibitor molecules
within the pit sides resulting in the reduction of inhibitor performance and
consequential increase in the propagation activities [7 , 133] .
Consequently , after the phosphate ester concentration increased to SOppm and

100ppm, the artificial pit depth s were reduced to 45 .6 11m and 37.4 11m . It is
interesting to compare the pit depth of the artificial pit and natural pit on the surface.
as they are in good agreement in term s of the reaction towards the action of the
inhibit or.
14 1
a) "~. b)
"",
02
0"
00 30
2')
06
20
,~
.
, 2
'0
,
c) d)
! -" • .... ~,
e) f)
X Profil e
. x 62 4 um
'V
~ 'Y
300
,
. -, ,"""-
hi'........... -w"--~_-v"l;I.".,)
~, j- ~1
'-"\ ,
r '~
200
f L.
"- ,
I ..,
100
um \ )
Ii jJ
100 200 300 4()0 500 595 0 ,.., :~
"" ' 00 '00
Figure 8- 14: Profilometer image of artificial pit on X65 carbon steel in CO 2 saturated
10% NaCl brine at 80°C , pH 5.65 , 1000ppm Fe 2+ and 1 bar total pressure with
phosphate ester inhibi tors; a) 2D view of pits surface at 200ppm, b) 3D view of pits
surface at 200ppm, c) 2D view of artificial pits surface at 200ppm , d) 2D view of
artificia l pits sUlface at 200ppm, e) 2D view of pits surface at 25ppm , f) 2D cross-
section of artificia l pits at 25ppm.
142

lmidazoline slows down the pitting propagation at lower concentrati ons and
the inhibitor performance will decrease if an overdose of inhibitor is appli ed. Figure
8-15 shows the comparison in pit depth results for the artificial and natural pits on the
sUIi'ace with different concentrations of imidazoline . The pit depth slows do wn to
23 .8/-1m with 25ppm of imidazoline and as the inhibitor increased to 50ppm, the
performance increased by decreasing the pit depth to 2l.1 /-I m . lmidazo line performed
at the optimum level at 100ppm by completely controlling the pitting attack wit h a pit
depth recorded at 11.5/-1m, as shown in Figure 8-16(a-d). However, wi th 200ppm
imidazoline, the artificial pit propagated to 68 .7/-1m as sho wn in Figure 8-16f, whi ch is
significantly higher that the blank test. It is postulated that thi s is due to an overdose
effect. The interaction was due to the excessive inhibitor molecule s enh ancin g the
chemistry within the pit site resulting in the reduction of inhibitor performance and
consequential increase in the propagation activities [7 , 133]. The artificial and natural
pits on the surface show that the pit depth trend is similar. These simil ar trends
indicate that the pitting activities and the reaction with the inhibitor are comparable
between the artificial pits and natural pits.
120
100
80
E
::i 60
-'=
~
Q.
(l) 40
0
Cl..
20
0
0 20 40 60 80 100 120 140 160 180 200
Inh ib i tor Co ncen t ra t io ns (pp m)
-+- M JX Ar t lfi ciJ I Pit - ..... - Ave Ar t lfici JI Pit
Fiaure 8- 15 : Artificial Pit Depth of X65 carbon stee l in CO 2 saturated I09'c NaCI
brine at 80°e, pH 5.65 , 1000ppm Fe 2+ and 1 bar total pre ss ure wi th imid azo lin e.
143
a) ,_ b)
o,
i
c) d)
".. "." '.

)" ~ ...
e) f)
""
05 I ~
2 "''''
'0
.l()
,.;}
:,
30
00
10
Figure 8-16: Profilometer image of artificial Pit on X65 carbon steel in CO=,- saturated
10% NaCI brine at 80°C, pH 5.65, 1000ppm Fe='- + and I bar total press ure with
imidazoline inhibitor; a) 2D view of pits surface at 100ppm, b) 3D view of pits
surface at 100ppm, c) 2D view of artificial pits surface at 100ppm, d) 3D view of
artificial pits surface at 100ppm, e) 2D view of pits surface at 200ppm, f) 3D cross-
section of artificial pits at 200ppm.
The natural pits propagate severely to 76/lm on the surface with 200ppm
imidazoline, the natural pit delayed propagation do wn to 7.8/lm with 100ppm
imidazoline.
144
8.4 Fourier transform infrared (FTIR) spectroscopy

IR reflectance spectra in the region 600 to 4000 cm- l were collected with
Perkin Elmer model spotlight 400. The objective of the test is to understand the
mechanisms of the inhibitor interaction with the surface in the pit region and outside
the pitting region. A background reflectance of a gold electrode was performed as a
reference before measurements were made on all test specimens. A complete
summary of the spectra assignments is shown in Table 8-1.
Wavenumber Peak assignment References

(em-I)
Corrosion
products
1638.4 (R-S-hC=O stretching of FeC0 3 [162, 164,
167, 184]
874.62 (R -S-hC=O stretching of FeC0 3 167
Inhibitor A
Component 1
2956.91 O-CH3 ester group from methanollCH 3 alkanes [159,161,
182]
2928.27 O-CH3 ester group from methanol/CH2 alkanes [159,161,
182]
2874.20 O-CH3 ester group from methanol/CH3 alkanes [159, 161,
182]
Component 2
1145.86 (CH3-0)3P trimethylphosphite CH3 group / alkyl [182, 183]
ethers
1120.00 (CH 3hP(OhNa dialkylphosphinate salts [183]
Inhibitor B
Components 1
3350 Aromatic amide (bonded NH) [159,182,
184]
Component 2
3030 CH=CH alkenes / acid amino [159, 182]
2855 CH 2 alkanes [159, 182]
Component 3
1675 Amide and imide/nitrites [159, 182]
1423 Fatty acid amine/CH 2/phenols [159, 182]
..
Table 8-1: FTIR spectra aSSIgnments for sweet condItIon
145
Figure 8-17 shows the spectrum obtained from the blank test after the test and
after the film was removed by Clarke 's solution. It can been seen that there we re two
peaks on the film and on the artificial pit, which were identified at 1638.4 cm· 1 and
874.62 em-I and are attributed to (R-S- )2C=O stretching, which cOlTesponds to iro n
Carbonate [164,183]. These peaks were present on the film after the test but we re
absent after being remove by Clarke ' s solution.
B.O
7 .0
With o/ltfilm -pit
6.0
5.0
------ ------
%T
With film-pit
4.0
3.0
2.0
1.0
2000 1900 1BOO 1700 1600 1500 1400 1300 1200 1100 1000 90 0 BOO
Figure 8-17: FTIR analysis of X65 carbon steel in CO 2 saturated 10% NaCl brine at
o ,+
80 C, pH 5.65 , 1000ppm Fe- and 1 bar total pressure after blank test

Figure 8-18 shows the spectrum of the neat phosphate ester and the spectrum
obtained from the specimen diluted phosphate ester at 100ppm concentration in
distilled water. It can be seen that there were two distinctively strong peaks on the
1
neat phosphate ester spectrum. Those peaks were at around 2956 .91 cm- to 2874.20
em-I, which corresponds to O-CH3 from the ester and CH 3 from the meth anol, at
around 1145.86 em-I to 1120.00 em-I, which corre sponds to (CH 3-O)3 Ptrimeth yl
phosphate CH 3 group and (CH 3 h P(Oh Na dialkylphos phinate salts [161 , 183 ]. The
spectra for 25ppm, 50ppm , 100ppm and 200ppm specimens we re taken on the
surrounding film and on the artificial pits and the summary res ults are show n in Tab le
8-2 .
146
/'
- -,
120 \ ,~
'-{?::.fn lemper{/Iu ;'e\

~
~-
-
105 A I8(/'C \ (
-
\
90 Dill@!1al 8(/'C
--,
-----,
-1- ~_f -----4--- - ..
DillIll!{1 al room
-- - -
%T
75
60
lemp~f{Iturl!
\
/ 1'
~)
I" f /--
Ester group
_-1-
-_./~
45
Phosphate group
30 \
.- f
15 ~ rV
I
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600
cm-1
Figure 8-18: FfIR analysis of phosphate ester inhibitor in di ffe rent conditi ons.
Condition Component 1 Component 2
Pit Film Pit Film

25 ppm No No No No
50 ppm No No No No
100 ppm Yes No Yes No
200 ppm Yes No Yes No
Table 8-2: Summary FfIR results for phosphate ester inhibitor at different
concentrations after the test.
It can be seen that there we re several phosph ate ester matc hing peaks on the
artificial pit site but phosphate ester was absent on the surrounding film area , as
shown in Figure 8-19 and Figure 8-20. There were fairly strong peaks at around
2956.91 cm-I to 2874.20 em-I , which corresponds to the ester group and also a weak
peak at aro und 1145 .86 em-I to 1120.00 em-I, which correspond s to the phosph ate
group [18 2, 183].

147
24
\
21
Phosphate group
JOOppm
18
" I Ester group
I
15
% T 12
200ppm
6 - ~----- r-- -
3 -------,. _ ~ __ ~ .-lllJllIk __ SOppm
2 sjip-",-- -
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 600
Figure 8- 19: FfIR analysis on the pit site area of X65 carbon steel in CO 2 saturated
10% NaCI brine at 80°C, pH 5.65 , 1000ppm Fe 2+ and 1 bar total pres sure with
phosphate ester in different concentrations.
24
21
Ph ospha te
Es ter group gro up
18
15
12
%T
9
3
--------------~~-------
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800
Figure 8-20: FfIR analysis on the film area of X65 carbon steel in CO 2 saturated 10o/c
NaCl brine at 80°C , pH 5.65 , 1000ppm Fe 2 + and 1 bar total press ure with phosph ate
ester in different concentration s.

148
Thi s shows that the inhibitor was attracted towards the pits rather than to the
surrounding film area. However, at lower phosphate ester concentrations of 50ppm
and 25ppm, pho sphate ester was absent on the pits site and the surrounding area .
Phosphate esters were absent due to the low concentrati on effect cause and did not
inhibit at the pit si te area.

Figure 8-21 show s the spectrum of the neat imidazoline and the spectrum
obtained from 100ppm imidazoline diluted in di stilled water.
,
12
"~ - -----
Y
C)
\ -
\, Room ",""
Aroma ti c amid e I
105 \ I temperatllre \ \
I
I \
I \
90 I
I \
I
I" 2,;'
\ I
\-
75 Diluted at
%T
60
\ 8(/'C
\
45 C H 2 a lkan es Amid e and imid e
group
30
100ppm
15
50ppm
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600
cm- 1
Figure 8-21: FTIR analysis of imidazoline inhibitor in difference condition s.
It can be seen that there were three di stincti vely strong peaks on the neat
imidazoline spectrum. There were fairl y strong peaks at around 3285 em-I to 3350 cm-
I, which corresponds to Aromatic amide, 2855 em-I to 3030 em-I , which corresponds
to fatty acid amide and also a peak at around 1423 em-I to 1675 em-I, whi ch
corresponds to the amide and imide group [159, 182, 184] . The spectra for 25ppm ,
50ppm, 100ppm and 200ppm specimens were taken on the surrounding film and on
the artificial pit s and the summary results are shown in Table 8-3 . During the scan on
100ppm and 50ppm specimens, these three major components of imidazoline peak s
were detected on the pit sides and the sUITounding film , as shown in Figure 8-22 and
Figure 8-23 . However, none of the peaks was found in the 200ppm and 25ppm
spec im ens due to the concentration effect. It is interesting that the inhibitor was found
149
both on the pit sites and the surrounding fi lm , wruch indicates that the irnidazoline
will form an adsorbed surfactant monolayer or bilayer on the surface of the metal to
protect the surface from corrosion.
Condition Component 1 Component 2 Component 3
Pit Film Pit Film Pit Film

25 ppm No No No No No No
50 ppm Yes Yes Yes Yes Yes No
100 ppm Yes Yes Yes Yes Yes Yes
200 ppm No No No No No No
Table 8-3: Summary FTIR results for imidazoline inhibItor In different concentratlOns
after the test.
120 ,
~"- ~~
:\
105· \ /~
I
/ Inhibitor
I
'- / "'- ,/ \ I
"\ \ I
I
' \\
, ,I
I
\ ,.I
I r
\j \ ('- ' \
75'
I
%T
I
60 \ I
F a tty ac id a mid e II /
45- IV A mid e a nd imid e gro up
I
30-
15
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600
em-'
Figure 8-22: FTIR analysis on the pit site area of X65 carbon steel in CO 2 saturated
2
10% NaCl brine at 80°C , pH 5.65 , 1000ppm Fe + and 1 bar total pres sure with
imidazoline in different concentrations

150
1675, 142 3 Amide

12
''''- and Imide group ,_
-
-
0/
~
,, - -. "'r
~/-'''- ,
105 I
I
Illhibitor
90 \
\ //\ /
IJ (,-,j
%T
75
II I.
60 C H , a lk a n es
Aromati c I
45 1\,--
(,
30 JOOpp
j.. \
,
I
15 ,.~
-800 - ---
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 600
em"
Figure 8-23: FfIR analysis on the film area of X65 carbon steel in CO 2 saturated 10%
NaCl brine at 80°C, pH 5.65, 1000ppm Fe 2+ and 1 bar total pressure with phosphate
ester in different concentrations
8.5 Summary
This chapter show s that the potentiostatic approach on artificial pits all ows the
artificial pit to propagate to around 48 .9flm to 53.1flm depth . Both phosphate ester
and imidazoline inhibitors showed excellent performance to stop pit propagati on if
optimum concentrations are applied. The in-situ camera observed that pit propagati on
is due to a black deposit forming on the surface and covering the artificial pit s, whi ch
results in a fa vourable condition for pits to grow . The FTIR analysis indicated that the
phosphate ester inhibitor inhibits pits by absorbing the inhibitor at the pit si te and the
imidazoline inhibitor inhibits the pits by absorbing the film.
151
Chapter 9: Evaluation of inhibitor performance using artificial pit

technique under sour conditions
In the previous chapter, the perfonnance of inhibitors was evaluated under

sweet conditions. This chapter uses the same techniques developed for testing in
sweet conditions and adapt the technique for the sour conditions. The artificial pit
growth on X65 carbon steel surfaces in sour conditions was assessed using the in-situ
monitoring technique. Nonoxynol-6 phosphate and poly alkyl pyridines single
components from corrosion inhibitors were used. Inhibitors were evaluated in tenns
of artificial pit propagation using electrochemical methods, which was supported by
post-test analysis. Assessment of the pit chemistry by FTIR analysis was used to
characterize the surface and profilometry analysis was used to detennine the pit depth.

Electrochemical corrosion measurements usmg DC linear polarisation
resistance measurements were carried out to monitor the corrosion rate during the
formation of the iron sulphide film in the first 2.5 hours. The corrosion rate after 0.5
hours purging with the sour gas in the solution was typically 1.5 mm/yr. The
corrosion rate dropped after 1.5 hours to 1.25 mm/yr, which is indicative of the
formation of an iron sulphide film on the surface. After 2.5 hours, the corrosion rate
dropped to 1.0 mm/yr, as shown in Figure 9-1, which indicates that the fonnation of
iron sulphide provides a protective film on the surface.
After 3 hours, electrochemical corrosion measurements using a potentiostatic

test were carried out to apply a constant electrode potential at 100m V more positive
than the free corrosion potential to activate the artificial pit on the surface to a desired
pit depth. Figure 9-2 presents the potentiostatic results for two experiments without
inhibitor. It shows that in the first blank specimen the current initially dropped from
3.5mA to 0.75mA for the first 45000s (12.5 hours) followed by a sharp rise to 2mA
until 57600s (16 hours) and was then held constant until the end of the test. The
second blank specimen started with a very sharp rise of current to 3.5mA and then a
decrease to 2.5mA at 1000s (0.25 hours), and, slowly, a further decrease to 2mA at
the end of the test.
15 2
Both specimens reached the hi gher current at 3.5mA , and have a long slow
current interval and achieve 2mA current at the end of the test. The current variation
could not be avoided with such a long expo sure time , which involved film formation
and changes of the kinetic s of the iron sulphide film with time . The current represents
the general dissolution behaviour of the surface , whi ch is influenced by the film
breakdown proce ss of the iron sulphide film.
2
...>,
~
] 1. 5
L
1
'-"
(l) ----_ T
~
....
c
.S
v;
---..
1
...
0
0
U 0.5
o 0.5 1.5 2.5 3
Time (hour)
Figure 9-1: Corrosion rate versus time for the first 2.5 hour on X65 carbon steel in
10% NaCI brine at 80°C and 10% H 2S, 90 % CO 2
0.004
..--- 0.003
<r:
'-'
......
c 0.002
OJ
........
::3
U 0.001
0
10 100 1000 10000
Time (s)
-+- Run 1 ---.- Run 2
Figure 9-2 : Potentiostatic polali sation curve at 4 hour to 24 hour on X65 carbon steel
in 10% NaCI brine at 80°C and 10% H 2 S, 90% CO 2 .
15 3
9.1.1 Effect of nonoxynol-6 phosphate

The perform ance of nonoxynol-6 phosphate inhibitor has been studied by
adding different concentrations at the start of the experiments. Electrochemical
corrosion measurements using DC linear polari sation resistance were carried out to
monitor the corrosion rate with nonoxynol-6 phosphate inhibitor in the firs t 2.5 hours.
There was a significant reduction in the corrosion rate in the presence of nonoxyno l-6
phosphate inhibitor. The corrosion rate dropped to 0.5 mmlyr at 25ppm after 2.5
hours; it provided 50% corrosion protection to the surface. Increasing the inhibitor
concentration re sults in a further decrease in the corrosion rate. At 100ppm and
200ppm of the inhibitor, the corrosion rates after 2.5 hours were 0.35 mmlyr and 0.25
mmlyr, which provided 65 % and 75 % corrosion protection on the surface, as shown
in Figure 9-3. These results show that the presence of the inhibitor appeared to
provide a protecti ve film on the surface to reduce the corrosion rate .
...
c
o 0.5
ZJ
o
'-
o
----
~
-- ----- --
U o
o 0.5 1.5 2 2.5 3
Time (hour)
-+- Bl ank ~ 2S ppm I OOppm ~ 200ppm
Figure 9-3: Corrosion rate versus time for the first 2.5 hours on X65 carbon steel in
10% NaCI brine at 80 DC and 10% H 2 S, 90% CO 2 with nonoxynol-6 phosphate
After 3 hours, electrochemical corrosion measurements using a potenti os tatic

test were carried out to apply a constant electrode potential at 100m V more positi ve
than the free corro sion potential to activate the artificial pit on the surface. Figure 9-4
presents the potentiostatic re sults for experiments with nonoxynol-6 phosphate
inhibitor. It sho ws that at 25 ppm and 100ppm the current is reduced to 1rnA and
0 .1rnA and the current maintained a steady value throughout the experiment.
However, at 200ppm the current had an initial ri se to 4mA at 18000s (5 hours)
followed by a slow decrease to 3mA and a slow increase again to 4mA at 50400s (14
154
hours). A fter that, the curre nt h ad a sharp ri se to 9mA at 57600s ( 16 hours) and
maintained a steady value before dropping to 8.5mA at the end of the test. The
increase in the current from the start at 1rnA and fi nish at 8mA indicates that the
surface w as c hanging towards an unprotec ti ve film over time.
0.0 1
~
0.008
<t::
'-"'
0.006
c(1)
..... 0.004
.....
::l
U 0.002
0
10 100 1000 10000
Time (s)
--*- blank -+--- 2S ppm --- 200ppm ---- 100ppm
Figure 9-4: Potentiostatic p olari sation curve s fo r 24 hour tests on X65 carbon stee l in
10% N aCI brine at 80°C and 10% H 2 S , 90% CO 2 w ith nonoxynol-6 phosphate
Fi gure 9-5 presents the fin al curre nt effec ts on inhibitor concentrati ons. It
show s that the final current at 25ppm and 100ppm inhibitors are lower than the test
w ithout inhibitor, however, whe n the inhibitor concentration increases to 200ppm , the
fin al current is higher than the test wi thout inhibitor.
9 -
8 - •
71
----
«
E 6-
'---'
~
c(1)
5-
t 4-
::l
U 3 -
~
.
c 2 • ,
Li: 1- -• -
0 .. .. - .. .. . . '
40 60 100 120 140 160 180 200

-1 D 20
Inhibito r concentrati o n (ppm)
F ig ure 9-5: F ina l potent iostatic current after 24-h our te st on X65 carbon stee l in 10o/e
NaC I brine at 80°C and 10% H 1 S , 90 % C01 with nonoxynol -6 phos phate
155
Thi s shows th at nonox ynol-6 phosphate inhibitor lowers the current if the
effective concentration is applied ; however, overdose of the inhibitor co uld increase
the current.
9.1.2 Effect of poly alkyl pyridines

The performance of poly alkyl pyridine inhibitor was studi ed by adding
different concentrations at the start of the experiments. Electrochemical corrosion
measurements using DC linear polarisation resistance meas urements were carried out
to monitor the corrosion rate during the formation of an iron sulphide film with pol y
alkyl pyridine inhibitor in the first 2.5 hours . There were massive reductions in the
corrosion rates in the presence of poly alkyl pyridine inhibitor. The corrosion rate
dropped to 0.5 mm/yr at 25ppm after 2.5 hours and provided 50% corrosion
protection to the surface . An increase in the inhibitor concentration re sulted in a
dramatic decrease in the corrosion rate. With 100ppm and 200ppm of the inhibitor,
the corrosion rate after 2.5 hours was 0.05 mm/yr, which provided 95 % corrosion
protection on the surface, as shown in Figure 9-6. The se results show th at the
presence of the inhibitor appeared to provide a protective film on the surface, which
greatly reduced the corrosion rate .
.. ~~~
c
o 0.5 ~
'Vi
o
.....
~~
o o
U
o 0.5 1.5 2 2.5 3
Time (hour)
-+- Bl ank ~ 25 ppm 100ppm ...- 200ppm
Figure 9-6: Corrosion rate versus time for the first 2.5 hours on X65 carbon steel in
10% NaCl brine at 80°C and 10% H 2 S, 90% CO 2 wi th pol y alkyl pyridines
After 3 hours, electrochemi cal corrosion measurement s using a potenti ostati c

test were carried out to appl y a constant elec trode potential at 100mY more positi ve
th an the free cOITosion potential to ac ti va te the artificial pit on the surface . Figure 9-7
presents the potenti ostatic results for experiments with Nonoxynol-6 phosphate
156
inhibitor. It show s that at 100ppm and 200ppm there was a massive reducti on in the
current to 0.1 rnA and the current maintained a steady value throughout the
experiment. This current is very low indicating the pre sence of a protective film on
the surface, which is supported by a lower corrosion rate before the current was
applied . However, at 25ppm the currents increased to a much higher val ue , to 8.5 mA,
and were held constant throughout the experiment. Figure 9-8 presents the final
current effects on inhibitor concentrations.
0.01
,.-...
<t: 0.008
-......
'-"
t::
I!) 0.006
~ 0.004 .........
U
0.002
0
...
~
-- -
10
~ ~
--
100
~
1000
,
10000
-
Time (s)
--.- Blank --- 100ppm --+- 200ppm -+- 2Sp pm
Figure 9-7: Potentiostatic polarisation curves for 24-hour test on X65 carbon steel in
10% NaCI brine at 80°C and 10% H 2S, 90% CO 2 with poly alkyl pyridine
9
8
7
~
E 6
'-'
C 5
I!)
t: 4
~
u 3
I'
~ 2 •
I:
LL: I ,
0
,
- ------------ - . -
- I {}r---~20~--~4~Or---~60~--~8~O----~IO~Or---M
I 2~O--~1~4ftO--~1~60
~--~~r___7DO
Inhibitor concentratio n (ppm )
Figure 9-8: Final potenti ostatic current after 24-hour test on X65 carbon steel In
10 %NaC I brine at 80°C and 10% H 2S, 90% C02 with poly alkyl pyridine
15 7
It show s that the final current at 25ppm inhibitor is hi gher than the test without
inhibitor, however, when the inhibitor concentrati on increased to 100ppm and
200ppm , the final current was lower than the test without inhibitor. Thi s shows that
poly alkyl pyridine inhibitor reduces the current after it reaches the minimum effec t
concentration, which under the conditions in the study is 100ppm.
9.2 In-situ camera monitoring techniques.

Figure 9-9 shows an early stage image after the specimen was immersed into
the solution. It clearly reveals that the formation of iron sulphide film took pl ace over
the surface within 1 hour after purging the sour gas. The iron sulphide film build up
started in the first 5 minutes , as shown by a darkening of the surface. The surface
continued to darken and eradicated the grinding lines, and after 30 minute s little of the
original surface could be seen. After the film covered most of the surface, the film
started getting thicker and took place over the artificial pit, as shown at 60 minutes.
The surface and the solution continued to darken and affect the ability of the camera
to continue monitoring the surface activity.
Figure 9-9 : In-situ image of X65 carbon up to 60 minutes on X65 carbon steel in 10%
NaCI brine at 80°C and 10% H 2S, 90% CO 2 ; a) 5min, b) lOmin , c) 20min , d) 30min, e)
45min , f) 60min
158

Figure 9-10 show s the effect of nonoxynol-6 phosphate inhibitor when it is
pre sent at 100ppm and 200ppm concentrations in the soluti on. No noxyno l-6
phosphate inhibitor in solution changes the solution to a milky co lour when it is
present at high concentration. At 100ppm, the inhibitor delays the fo rmati on of the
iron sulphide film . The surface can be observed until 4 hours. The formation of iron
sulphide is much less at 4 hours compared to the specimen without inhibitor. After 4
hours, the solution started to darken and affected the ability of the camera to co ntinue
to monitor the surface activity . The camera was unable to monitor the ac ti vity on the
surface when 200ppm of nonoxynol-6 phosphate inhibitor was added due to it
changing the solution to a milky colour, as stated .
a ) 100ppm (0 1h )
Figure 9-10: In-situ image of X65 carbon steel in 10% NaCI brine at 80°C and 10%
H 2S, 90% C02 with nonoxynol-6 phosphate; a) 100ppm at 0.1 h, b) 100ppm at 0 .5 h,
c) 100ppm at 2 h, d) 100ppm at 4 h, e) 100ppm at 5 h, f) 200ppm at 0. 1 h
9.2.2 Effect of poly alkyl pyridine

Figure 9-11 shows the effect of pol y alkyl pyridine inhibitor when it is prese nt
In 100ppm and 200ppm concentrations on the surface . At higher concentrations, the
inhibitor stops the formation of iron sulphide films on the surface and does not tum
the solution to a bl ac ki sh colour. At 100ppm, the inhibitor delays the format ion of
iron sulphide film up to 30 minutes, however, after th at the formation of the iro n
sulphide film for ms very quickl y and takes pl ace over the surface . After the
159
concentration was increased to 200ppm , the formation of the iron sulphide film is
seen to stop and it al so stops turning the solution blacki sh. The camera was abl e to
observe the artificial pit activity until the end of the experiment at 24 hours. The
surface grinding line s and some uncorroded areas still exi st and can be observed after
24 hours. A very thin corrosion product layer is seen to exi st across most of the
surface. There was no significant growth in pit diameter during the te st due to the
geometry of the artificial pits, which have a large diameter compared to the depth .
Figure 9-11: In-situ image of X65 carbon steel in 10% NaCl brine at 80°C and 10%
H 2S, 90% CO 2 with poly alkyl pyridine ; a) 200ppm at 0 .1 h, b) 200ppm at 2 h, c)
200ppm at 24 h, d) 100ppm at 0.1 h, e) 100ppm at 0.5 h, f) 100ppm at 1 h
9.3 Pit depth analysis

The blank test was carried out to assess the severity of the te st condition and to
enable evaluation of the performance of the inhibitor. The specimens were anal ysed
by measuring the artificial pits on the specimens surface as well as the three deepe st
natural pits with the purpose of trying to detect the most significant pits that create
failure . The profilometer analysis shows that after 24 hours of blank te st the average
artificial pits propagate from 9/lm to around 31 .6/lm , howe ver, in some blank sampl es
the maximum artifici al pit depth obtained is 34.9/lm , as shown in Figure 9-1 2(a-f).
160
a) 0 3 ~
• "., b)
" 1 m",
O~ ~~
I
2~ 5
" ?O
2~
" ":1
3 ~ , ~
~
, ~ ~
45
~
'0
55
75
05
~ ~
7,
9 0
c) d)
X Pro file
22 4
..,. : S8 ) um
'<:7
150
I
100
50
I
50 100 150 200 2 ~0 295
e) f)
Y Profile
Figure 9-12: Artificial pit depth of X65 carbon in 10% NaCI brine at 80°C and 10%
H 2 S, 90% CO 2 after the blank test; a) 2D vie w of pits surface , b) 3D view of artificial
pits surface, c) 2D View of artificial pits surface, d) Cross-section view x-profil e of
artificial pits surface, e) 3D view of artificial pit s surface, f) Cross-section view y-
profile of artificial pits surface.
The potenti al applied to the surface also initiates and propagates other natural
pits on the SUITounding surface . The three deepest natural pits detected on the surface
were within the range of 22.2 /-lrn to 49.3/-lrn and the average natural pit detected on
the surface was 34.3 /-l rn .

161

Nonoxyno l-6 ph os phate slows do wn the pittin g propagati on at 2Sppm and
100ppm , ho wever, the inhibitor perform ance decreases after 200ppm of inhibi to r is
applied. Figure 9-13 shows the compari son in pit depth results for the arti ficial a nd
natural pits on the surface with different concentrati ons of nonoxynol-6 phos phate.
120 - - - - - - - - - - - - - - - -- -- - - - - -________________________________
100 - - - - - -- - - - - -- - - - - - - - - - - - - - - - - -______________________~
~ 30 - - - -- - - - - - - - - - - - - -- - - - - - - -______________________~~~----
E
::::l.
o 20 40 60 30 100 120 140 160 130 200

Inhibitor concentrati on (ppm)
-+- M ax Arti ficial Pit -+- A ve Arti ficial Pit
M ax N atural Pits --e- A ve Natural Pits
Figure 9-1 3: Pit depth analysis of X65 carbon steel in 10% NaCI brine at 80°C and
10% H 2 S, 90% CO 2 with different concentrations of nonoxynol-6 phosphate
At 25ppm of nono xynol-6 phosphate the artifi cial pit depth IS slowed to
18.811m and as the inhibitor increased to 100ppm , the perform ance performed at
optimum level by completely controlling the pitting attac k with a pit depth recorded
of 13.2I1m , as shown in the 3D image in Fi gure 9-1 4(a-d ).
However, at 200ppm of nonoxynol-6 phosphate inhibitor the artificial pit

propagated to 11 311 m , which is significantly higher than the blank tes t and is
attributed to an overdose effect as shown in Figure 9-1 4f.
162
a) b)
,.
t. !T.tTI
0
05
10
15
,.
" "
10
'3 ~)
.,
"
c) d)
e)• •0 ~r--::I""""""""""" __---"_- __ f)

X Profile
x 01 8 2mm
0 75 ..,
~
060
j~ 1ti~t ,1
046
0 30
0 15 .........,. , -
i;
1.0 1.2
~~~~~~~~~~J
,..0
Figure 9-14 : 3D image of profilometer analysis of artificial pit on X65 carbon steel in
10% NaC I brine at 80°C and 10% H 2S, 90 % CO 2 with nonoxynol-6 phosphate ; a) 2D
view of pits surface at 100ppm, b) 3D view of natural pits surface at 100ppm, c) 2D
view of artificial pits surface at 100ppm, d) 3D view of artificial pits surface at
100ppm, e) 2D view of artificial pits surface at 200ppm, f) 20 cross-sec ti on of
artificial pits at 200ppm.
The interaction was due to the exceSSIve inhibitor molecules enhancing the
chem istry within the pit site, which resulted in the reduction of inhibitor performance
and consequent increase in the propagation ac ti vitie s. The natural pit on the surface
show s th at the pit depth for 25ppm is 66 . 1 flm , whi ch is significantl y hi gher th an the
bl ank specim ens and has an opposi te effect compared to the artifici al pits on the
163
surface. The performance of the inhibitor at 25ppm is attributed to the underdose

effect and in the tran sition region towards inhibiting the surface. The trend for natural
pits for 100ppm and 200ppm show a similar effect to the natural pits where the
natural pits detected were 12f.lm at 100ppm and 117f.lm at 200ppm .

The introduction of poly alkyl pyridines into the experiment can control the
pitting propagation if the required amount of concentration is applied. Figure 9-15
shows the comparison in pit depth results for the artificial and natural pits on the
surface with different concentrations of poly alkyl pyridines .
160
140
/"""'0-
120
6
::i. 100
'--'
...
...c:
0... 80
(!)
...
'"0
......
p....
60
40
20
0 - - -a
0 20 40 60 80 100 120 140 160 180 200
Inhibitor concentration (ppm)
--+- Max Artificial Pit --+- Ave Artifici al Pit
Max Natural Pits - . - Ave Natural Pits
Figure 9-15: Pit depth analysis of X65 carbon steel in 10% NaCl brine at 80°C and
10% H 2S, 90% CO 2 with different concentrations of poly alkyl pyridines.
At 200ppm of poly alkyl pyridines it can slow down the artificial pit
propagation process to 11.2f.lm, as shown in the 3D image in Figure 9-16(a-d).
However, with 25ppm poly alkyl pyridines, the artificial pits propagate to 146f.lm,
which is significantly higher than the blank test as shown in Figure 9-16f. Thi s is
attributed to be caused by the lower adsorption of the inhibitor molecule s within the
pit sides resulting in the reduction of inhibitor performance and consequenti al
increase in the propagation acti vities [7 , 133] .
164
a) b)
a !. 6 '} IT IT
os
"
, 5 "
:5
~ ~
.,
55
/
0'
I c) d)
/
I I ;.'
" . .i
'i ,"
..,~. '"
r,., .~•
.,
e) f)
u ~o
Y Profile
o 7~
060
046
0 .30
o I~
mm
0.00
0 .0 01 04 06 08 10 11
Figure 9-16 : 3D image of profilometer analysis of artificial pit on X 6S carbon stee l in

10% NaCI brine at 80°C and 10% H 2S, 90 % CO 2 with poly alkyl pyridi nes; a) 2D
view of pits surface at 200ppm , b) 3D view of natural pits surface at 200ppm , c) 20
view of artificial pits surface at 200ppm , d) 3D view of artificial pits surface at
200ppm , e) 2D view of artifici al pits surface at 2Sppm, f) 2D cross -sec ti on of arti ficial
pits at 2Sppm.
Consequentl y, whe n the poly alkyl pyridines concent rati on increased to

100ppm the artificial pit depth reduced to 16 f.lm . It is interesting to compare the pi t
depths of the arti ficial pit and natural pit on the surface, whic h are in good agreement
in term s of the reacti on towards the inhib itor. The natural pits detected at 200ppm
we re 6.48 f.lm , whi c h shows th at the po ly alkyl pyridines fully control the loca li ed
act ivity on the surface . T hese simil ar tre nds indic ate that the pitting ac ti viti es and the
165
reaction with poly alkyl pyridines are comparable between the artificial pits and
natural pits.
9.4 Fourier Transform InfraRed (FTIR) Spectroscopy

IR reflectance spectra in the region 600 to 4000 cm- I were collected on the
surface after the test. A complete summary of the spectra assignments is shown in
Table 9-1.
Wavenumber Peak assignment References

(em-I)
Corrosion
product
3432 H-O stretching refer to [159]
3370 H-O stretching respectively refer to [ 159]
mackinawite
3250 Precipitation of Fe(II) as FeC0 3 [166]
2900 FeS [ 169]
2343 C02 asymmetric stretching [164, 168]
2198 CO 2 asymmetric stretching [164,168]
1621 H-O stretching refer to mackinawite [156,173]
1364 FeOOH with adsorbed of carbonate [162]
1000-1245 Polythionates assigned to pyrite [172]
665 Fe-O and Fe-OH to mackinawite [156]
Inhibitor C
3000-3500 C-H stretching refers to aromatic amine or [159, 182,
phenol 183, 184]
2959 O-CH3 from ester group [159,161,
182,183,184]
1725 C=O stretching of fatty acid amine [182,183,
184]
1377-1610 CH3 and CH2 scissor [182,183,
184]
1111-1377 (CH3-0h ptrimethlyphosphateand [182,183,
(CH3hP(Oh nadialkylphosphinate salts 184]
Inhibitor D
2800-3500 C-H stretching refers to aromatic amine or [159,161,
phenol 182, 183, 184]
2242 Nitrile substituted amine salts, alkynes, [182.183,
deuterated aliphatic 184]
1377-1472 Carboxylate salt of CH3 and CH 2 [161 ]
662-1028 C-N assignment to ketone, amude and [182,183,
aromatic aldehyde 184]
..
Table 9-1: FTIR spectra aSSIgnments for sour condItIOn
166
/ . - .-
\\
125
115 \
\
105 \
\
\
I
95
\ I
85
\
\
%T 75 \
\ I
\ I J
I
\
65 \ Film
\ I
I
"-~
55
'\ \
\
45
'"'\
~
I
35 I
Pitting
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800
eM ·1
Figure 9-17 : FTIR analysis on X65 carbon steel in 10% NaCI brine at 80°C and 10%
H 2S , 90% CO 2 .

Figure 9-18 shows the spectrum of the neat nonox ynol-6 pho sphate and the
spectrum obtained from 100ppm nonoxynol-6 pho sphate diluted in distilled water at
SO°c. It can be seen that both spectra po ssess several matching peaks, however, the
spectra after being diluted is weaker and some peaks are absent. A di stincti vely large
peak is identified at around 3498 em-I, which corresponds to the C-H stretching band
that is usually present between 3000-3500 em-I, which is ass igned to aromatic ami ne
or phenol functional group [161 , 159, 161 , 183, 184, ISS] . Another large pe ak is
identified at 2959 em-I, which represents the O-CH3 ester group from the methanol
[159 , 161]. A peak at 1725 cm- l represents the C=O stretching band of carbonyl peak ,
which is indicative of the carboxylic acid functionality of fatty acid ami ne [159 , 161].
l
The appearance of a peak around 1377-1610 cm- is due to inorganic carboxylate salt,
which is probably due to CH 3 and CH 2 sc issor [182]. The broad peaks around III 1 -
1377 cm-l cOITespond to the (CH 3-O)3 ptrimethyl phosphate CH 3 gro up and
(CH 3 ) 2P (O h nadialkylphosphinate salts [183 , 184] . Some of the peaks cannot be
conclusively assigned to a particular functional group as the inhibitor acti ve
component is just a 10% mixture in methanol.
167
12
105 I Diluted at 81/'C
90 ~ I
75
E lho x yel h y l a m lOe
o r a lk y l gro up
%T
60 Amin o
Aro m atic a min e s ub sti tu ted
A ro m at ic a m ine n r phe n o l
4 Ph o ~p h 3le gro up
Room temperetllre
~-~
2800 2400 2000 1800 1600 1400 1200 1000 800 600
cm -1
Figure 9-18: FTIR analysis on nono xynol-6 phosphate inhibitor for different
conditions.
The spectra for 25ppm , 100ppm and 200ppm spec Imen s were take n on the
surrounding film and on the artificial pits and the summary results are shown in Table
9-2. It can be seen that there were several nonoxynol-6 phosphate matching peaks on
the artificial pit site and the surrounding film area for 25ppm and 100ppm speci mens
but nonoxynol-6 phosphate was absent on the surrounding film area fo r 200ppm
specimens, as sho wn in Figure 9-19 and Figure 9-20.
Condition Inhibitor
absorption
Pit Film
25 ppm Yes Yes
100 ppm Yes Yes
200 ppm No No
Table 9-2: Summary FTIR results for nonoxynol-6 pho sphate inhibitor with different
concentrati ons.
168
75 .5
65
55
A rOlll a ti c
E th oxye th y l
a min e or
a m in e o r
45 Blank " h e no l a.lk y l g ro u p A ro m a ti c Amin o
a min e o r s ubs titu e nt
%T Pho s ph a te
Inhibitor ph e n o l
>A
grou p
35
I - ~~, t- -
2 IOOpP~
J15P~)
I
• ,,"~' :0
1
5 200ppm "l -V - '·"

4000 3600 3~2;;:::07::
0 ---;2:;;:;8~00;:;-----;::2::40;;-;0;-~~~
::::
20::::0:::0---=-1-:::-80~0~---:-1:-:
60:-::0-~1~4-:0-:-
0 --':::~1S20::::0-~1~0~0~
0 -~8~0~0--600
Fi gure 9-19 : FTIR analys is on the pit site area of X65 carbon stee l in 10% NaC I brine
at 80°C and 10% H 2S, 90% CO 2 with diffe rent concentrati ons of nonoxynol-6
phosphate
125
\ ,
110 Blank Elh oxyelhyl
amIne or
\ alkyl group
\
90
I
Ph o s pha te
\ Aromati c
\ grnu p
amine or ;
75 \
phenol
, I Amin o I
%T \
I ,'CO" substitu ent I
55
I OOppm
-~, I ,
m
_o_- , "
\
f
40 -~ 25 ~
Pp
'\
Inhibitor -
\ I "",- , /r /
25 \
\
"
(0 v
?f'y -
,,,:
G,..---"~;·· /'
10 200ppm \~
-------------~~-------------~
4000 3600 3200 2800 24 00 2000 1800 1600 1400 120 0 1000 800 600
Figure 9- 20: FTIR analysis on the film area of X65 carbon steel in 10% NaCI brine at
80°C and 10% H 2S, 90% CO 2 wi th different concentrations of nonox ynol-6 phosphate
There were stro ng inhibitor peaks detected in the area of the pits for 100ppm
spec imens, which we re at aro und 3356 em- I, 2974 em,l, 1609 cm,l, 1473 cm'l and
1260c m' l. For the same specimen s, stronger inhibitor peaks were detec ted on the fi lm
169
1610 cm- I and 1244 cm- I. It can be seen that there are several
I
area at 2961 cm- ,
matching inhibitor peaks between the pit area and the film area, which confirms that
the inhibitor was present in both areas. A direct comparison between the 100ppm
specimens and the blank specimen can only be made at the weak inhibitor peak area.
There were strong peaks detected at 2198 and 1097cm- 1 representing corresponding to
CO 2 asymmetric stretching and polythionates respectively refers to pyrite [172, 164,
168].
There were weak inhibitor peaks detected at the pit area for the 25ppm
specimen, which were at around 3498 cm- I , 1473 cm- I, and 1156 cm- I. On the same
specimens weak inhibitor peaks were detected in the film area at 1268 and 1153.23
cm- I. Several matching inhibitor peaks between the pit area and the film area confirm
that the inhibitor was present in both areas at 25ppm, but the lower concentration of
the inhibitor affected the absorption to the surface. There is also a matching peak for
pyrite found on the film area at 1030 cm- I. This shows that at effective level dosing,
nonoxynol-6 phosphate was found both on the pit site and the surrounding film to
provide an adsorbed surfactant monolayer or bilayer with iron sulphide film on the
metal surface to provide a protective film.

Figure 9-21 shows the spectrum of the neat poly alkyl pyridines and the
spectrum obtained from 100ppm poly alkyl pyridines diluted in distilled water at
80°C. It can be seen that both spectra possess several matching peaks and the spectra
after being diluted still detects a strong signal and is not affected by the dilution
process. A distinctively large peak is present between 2800-3500 cm-I, which
corresponds to the C-H stretching band, which usually refers to the aromatic amine or
phenol functional group [159, 161, 182, 183, 184]. The large peak identified at 2242
cm- I represents the nitrile substitute, possibly amine salts, alkynes and deuterated
I
aliphatic [182]. The appearance of peaks around 1377 - 1472 cm- are due to
carboxylate salt, which is probably due to CH 3 and CH z scissor [182]. The broad
peaks around 1028 - 662 cm- I corresponds to C-N assignment corresponding to
carbonyl compound, possibly ketone, amide and aromatic aldehyde [183, 184]. Some
170
of the peaks cannot be conclu sivel y assigned to a particul ar functi onal gro up as the
inhibitor active component is just 10% mi xture in methanol.
The spectra for the 25ppm, 100ppm and 200ppm specimen s were taken on the
surrounding film and on the artificial pits. The summary re sults are shown in Tabl e 9-
3. It can be seen that there were several poly alkyl pyridine s with matching peaks on
the artificial pit site that were absent on the surrounding film for the 100ppm and
200ppm specimens, as shown in Figure 9-22 and Figure 9-23 . The bad spec tra signal
observed for the 25ppm specimen is due to the concentration effect and tenac iously
chemisorbed inhibitors.
Condition Inhibitor
absorption
Pit Film
25 ppm No No
100 ppm Ye s No
200 ppm Ye s No
Table 9-3 : Summary FTIR results for poly alkyl pyridines inhibitor at different
concentrations
Fairly strong inhibitor peaks were detected in the area of the pits for the
I
200ppm specimen, which were at around 2292 em-I, 1640 em-I , 1453 em-I, 1473 cm-
and 1103 em-I. Weak inhibitor peaks were detected in the area of the pits area for the
I
100ppm specimen , which were at around 3412 em-I , 1461 cm- and 824 em-I.
However, at both concentrations, 100ppm and 200ppm , poly alkyl pyridines were
absent for the surrounding film .
A direct compari son between the 100ppm specimen with the blank specimen
I
on the fi lm area show s that a peak was detected at 33 70 cm- and 1621 em-I,
corresponding to H-O stretching re spectively refer to mackinawite and a peak at 10 11
cm- I corresponding to polythi onates respec ti ve ly could refer to pyrite [ 15 6. 173.172] .
171
90
f) ilu ted at 8(f' C '

75 Carbo n y l
co mp o un d
60 N itri l e s ub s l i tll t e d
%T
45 -- I I 0 . \
\
30 '\ " " ''"''

4·b/ / R,;m"mp"","" \
=
' :>
. \-
C
\ I , ('" ..
15 \, -.:.r;-) -' \ : .\ . '~': - ~

~ ----~---------
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600
Figure 9- 2 1: FTIR analysis of poly alkyl pyridines inhibitor in differe nt conditions.
52.5
21111ppm
%T 28
46
34
o Cmbo n y l
c o mp o un d
22
4000 360 0 3200 2800 240 0 2000 1800 1600 14 00 1200 1000 800 600
em-'
Figure 9-22: FTIR analysis on the pit site area of X6 5 carbon steel in 10% NaC1 brine
at 80°C and 10% H 2S, 90% CO:2 with diffe rent concentrations of poly alkyl pyridines.
The compari son with the 200ppm spec imen shows that a peak is detected at
l
around 3250 cm-!, w hich could refer to FeC03 and a single peak at 2343 cm-
l
appeared due to CO:2 asymmetric stretching [1 68 ]. A peak was detec ted at 1364 cm-
and a single peak at 850 cm-!, whi ch onl y appeared on the 200ppm spec imen and was
absent on the inhibitor spectra and the bl ank spec tra. It coul d be FeOOH wi th
adsorbed carbonate or new fi lm that fo rm from the interac tion between the inhibitor
and the sour environment [162 , 166 ].
172
130
115 200l!!!!!!- _
,.,G,.
10 \
B/~nk
\
85
\
70
%T
55
40
25
10
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800
cm-1
Figure 9-23: FTIR analysis on the film area of X65 carbon steel in 10% NaCI brine at
80°C and 10% H 2S, 90 % CO 2 with different concentrations of poly alky l pyridines
9.5 Summary
Thi s chapter shows that the potentiostatic approach on artificial pits allows the
artificial pit to propagate to around 31/Jm deep . Both nonoxynol-6 phosphate and poly
alkyl pyridines inhibitors showed excellent performance to stop pit propagation if
effective concentrations were applied . The in-situ camera observed that an iron
sulphide film could cover most of the surface in 60 minutes. However, if effective
concentration of inhibitor is applied, it show s that the inhibitors ac tually stop the
formation of a black film , which could refer to iron sulphide . FTIR analysis indi cates
that the poly alkyl pyridines inhibitor inhibits pits by absorbing at the pit site and
nonoxynol-6 phosphate inhibitor inhibits the pits by absorbing on the film.
173
Chapter 10 Discussion
In the previous chapters detailed characteristics of sweet and sour films
followed by pitting behaviour and the effect of inhibition have been presented. In
order to understand the mechanisms of inhibition on pitting, this chapter will discuss
the formation of films in sweet and sour conditions that influence the localised pitting
attack and the mechanisms of individual component inhibitors to mitigate pitting
corrosion. This chapter is divided into three sections - section one discusses the early
stages of sweet film formation and the protectiveness on the film and discusses the
effect of sweet pre-corrosion under sour conditions. The second section will discuss
the initiation and propagation of pitting in sweet and sour corrosion and the
mechanisms of inhibitors on sweet pre-corrosion. The third section will discuss the
mechanisms of pitting and its inhibition based on the in-situ observation technique
and FfIR analysis in sweet and sour conditions.
10.1 Sweet film behaviour

In this section, there are four mam parts to discuss with respect to the
behaviour of the sweet film:
• X65 microstructure
• CO 2 corrosion mechanism
• Fe3C role in localized pitting
• FeC0 3 film build up
The microstructure of X65 carbon steel has large pearlitic eyes areas and a ferrite
phase with small grains [130]. Pitting initiation preferentially takes place in the
pearlitic areas where the uncorroded Fe3C phase is left behind from the anodic
reaction in sweet corrosion [130]. The early stages of sweet corrosion start with the
anodic reaction with the transfer of Fe 2+ ion from the surface to the solution. This
reaction leaves an undissolved Fe3C component from the steel that accumulates on the
surface [5, 29, 49]. Simultaneously, the cathodic reactions that take place release
C0 2- ion to the solution. When the solubility limit is exceeded then the iron
3
2
carbonate film precipitates. The solubility of Fe + is influenced by the pH of the
solution; pH values of more than 5 have a lower solubility. which corresponds to
174
higher supersaturations and accelerates the precipitation process of FeC0 3 [5]. This
will influence the time needed to reach a steady state condition in which the film
growth covers all the surface, as indicated by reaching a constant corrosion rate. The
types of film and the protectiveness of the film depend on whether the overall process
is governed by diffusion of the metal cation or by the perceptible anion [29]. The
FeC03 film will be protective if precipitation and redissolution are the majority
process, which is termed soluble, however, the film will be unprotective if the
diffusion in the liquid phase is predominant in which case the process is called
insoluble [29].
Figure 10-1 explains that the early stage of sweet film formation at 50°C,
I %NaCI with saturated CO 2 starts with the transfer of Fe 2+ ion from the surface to the
solution and leaves undissolved Fe3C on the surface. At 0.5 hours exposure time,
AFM shows that the thickness of the film is 1.4f.lm thick. This is 0.7f.lm thicker
compared to 0 hour, which leaves behind undissolved Fe3C from the anodic reaction.
This is supported by the EDX results that show that the reduction of iron content at
97.47% Fe compared to 98.19% Fe at 0 hour. Figure 6-19 shows the FIB-SEM
topography image after 0.5 hours corrosion. It shows that the empty uncorroded Fe 3C
phase creates a groove, which appears as a uniform attack with a rough surface. The
groove will then be filled with FeC0 3 film and the overall predominant process will
govern the protectiveness. This reaction will cause internal acidification, which will
change the local pH and local water chemistry and lead to the risk of localised pitting
attack. The FIB-SEM cross-section image in Figure 6-18 shows that at 0.5 hours there
are some porous or unfilled regions, which lead to unprotective film.
After I-hour exposure, there is FeC0 3 growth in most of the unfilled regions.
However, due to the pH of around 4, the solubility of Fe 1+ is high, which corresponds
to a low supersaturation, and, therefore, an insoluble type film forms. This is shown in
Figure 10-1 (iii), which is supported by the AFM results that show that the film
thickness is 1.5f.lm. It is interesting that the corrosion rate behaviour becomes constant
after 1 hour, recorded at around 3 mm/yr to 4 mm/yr, which is evidence that the film
reaches a steady state condition. In this condition, the film that grows is classed, as a
semi protective mixed type FeC0 3 and Fe3C film. However. the EDX relative
percentage data shows that the iron content in the films decreased as the films grew
175
thicker with time . Figure 6-22 sho ws that after the film reached a stead y state
condition, the film thickness increased linearly overtime until 4 hours; converse ly th e
iron content reduced linearly with time . Figure 6-23 shows th at the linear relation
between the film thickness and the iron content after I-hour exposure time .
-~\T-r=t.
Film Thickness
i)
T=O.7pm
Uncorroded
(as polished)
ii) - - • T- ,...----~................IIt················· · Im r Carhide

......... Mat@r I
T=1.4um
Early stage sweet corrosion
(0.5 hour)
_~t __ ,..__ ... Iron Carbide
T +t =1 . 5~lm
iii)
Later stage sweet corrosion

(After 1 hour)
Figure 10-1 : Early stage of sweet film formation.
The SEM images in Figure 6-8 show that at 4 hours the FeC0 3 film growth is
thicker with time , which is influenced by the texture of the Fe3C structure that it
leaves on the surface. However at 8 hours, the morphology of the film is seen to
change due to more FeC0 3 being produced on the surface compared to Fe 3C. The
morphology at thi s stage is changing by breaking the Fe3C structure, which is left
behind and whitish flake s scattered around the surface start to develop, as sho wn in
Figure 10-2. Thi s type of film morphology will develop and become thicker with
time.
After 24 hours of exposure time , the cross-section image in Figure 6-1 4 shows
th at the film growth is up to 23 /lm. Generally, the structure is not homogeneous and
the conte nt flaw s and pores are typic ally distIibuted over the entire thicknes . which is
in ag reement wit h the results of Schmitt e t aI. , who obtained the same morpho logy
176
with a 40fjm film thi ckness after 48 hours in simil ar experimental conditi ons [62].
The top view morphology in Figure 6-24 shows that the morphology of the film
re vealed two di strict phases consisting of flat dark grey region s that are porous fi lm
with scattered whitish fl akes forming a film around the surface , which indicates
FeC0 3 film and Fe 3C film . This is also supported by the XPS re sults, whi ch indicate
that the 2.S-hour specimen has Fe 3C and FeC0 3 elements on the surface .
. ....... Iron Co bor' ale

Film Thi ckness
• Iron Ca rbi de
i)
Malenal
T+t =2 .1pm

(After 4 hour)
.. __~ I ron C8 rbOf'8tB
............ ... ....... • I ron C;;mi e
.. .. ...• Ma:8nal
La ter stage sweet corrosion

(After 24 hour)
Figure 10-2 : Later stage of sweet film formation
The EDX data on the whitish fl akes type film are in agreement with Ruzic et
al. in their studies they prove that the EDX content of the whiti sh flakes type fi lm
indicates a pure FeC0 3 type film [42] . The film thickness in these studi es was
measured using three different technique s FIB , SEM, AFM and cross-section SEM.
The cross-section SEM technique is not very suitabl e to measure very thin film s th at
are less than 2 ~m , as the preparation process may damage the film , as the gap
between the resin , film and sub strate is very small.
177
10.2 Sour film behaviour

In this section, there are three main parts to discuss with respect to the sour
film behaviour:
• Sour corrosion mechanism

• FeS film build up
• FeC03 and Fe3C film in sour condition
The sour specimens were first pre-corroded in 1% sodium chloride at a

constant test temperature of 50°C in CO 2 saturated solution at atmospheric pressure
for 2.5 hours before being transferred to the sour experiment vessel at different
temperatures. On completion of the test at Baker Hughes laboratory, the specimens
were used in this study to analyse the film and understand the effect of the sweet pre-
corrosion at different sour temperature exposures. From the literature, a better
understanding of the mechanism of the sour film after sweet pre-corrosion and the
effect on the film morphology at various temperatures in sour environments need
further investigation and will be discussed in this section.
In sour environments, both iron sulphide and iron carbonate layers can form
on the surface of the steel. The formation of a film on the surface is the most
important factor governing the corrosion rate and depends primarily on the kinetics of
the film growth [125]. Hydrogen sulphide dissolution is about three times weaker than
carbonic acid, however, hydrogen sulphide gas is about three times more soluble than
carbonic acid. Hence, the effect of hydrogen sulphide and carbon dioxide decreasing
the solution pH is approximately the same [1, 5]. However, the level of hydrogen
sulphide in the solution will determine the kinetics of the film growth. At low levels
of hydrogen sulphide, it can act as a promoter of anodic dissolution through sulphide
adsorption and affect the pH and increase the corrosion rate by forming iron
carbonate. However, hydrogen sulphide can also reduce the corrosion rate by forming
a protective iron sulphide film, as the rapid kinetics of mackinawite formation
consume or complexes most of the Fe 2+ ions produced by the corrosion reaction when
the corrosion product could be iron carbonate [5, 113].
178
Iron sulphide formation can be either by direct solid state reaction between
hydrogen sulphide gas and the steel surface or by iron precipitation [24]. The
mechanism of this reaction will structure different types of iron sulphide, which
results in the formation of two different layers. The first layer usually shows the
presence of a very thin mackinawite film as a result of the direct reaction at the early
stage of film formation. The second layer of iron sulphide will form due to the iron
precipitation process and ionic conduction of S2., HS·, Fe2+, etc. through the
semiconductive mackinawite matrix. The cathodic reaction will be supported by the
conductive iron sulphide film on the other layer and the anodic dissolution of ferritic
iron will process beneath the film by solid state diffusion and leave the Fe 3C phase
with subsequent groove formation [24, 130]. In both cases the mechanical integrity of
the growing film is weakened due to the migration of Fe2+, which leaves a void at the
metal interface. This undermining process can develop internal stress, which leads to
film fracture causing potential localized corrosion [24, 125]. Figure 10-3 shows the
mechanism of the sour film formation.
i)
. . • Material
Iron Sulphide
..•........ ~ (First Layer)
ii)
....... Material
Earty stage sour corrosion Iron Sulphide

~Secood Layer)
........ Iron Sulphide
•••.••.•.. .......~ IFIl1>t Layer)
.. .---
'
iii)
------ ........................ Iron Carbioo
......... Material
Later stage sour corrosion
Figure 10-3: Sour corrosion film formation.

179
The literature has reported many types of iron sulphide that may form in sour
environments - amorphous ferrous sulphide, mackinawite, cubic ferrous sulphide.
smythite, greigite, pyrrhotite, troilite and pyrite [4]. The three main forms of iron
sulphide that are commonly found in the field include mackinawite, which is a
metastable form of FeS that forms in the presence of small amounts of hydrogen
sulphide [24]. The second species is pyrrhotite, which is believed to be more
thermodynamically stable than mackinawite due to the formation kinetics being much
slower [24]. Pyrrhotites will form as a sour corrosion product when the iron sulphide
level in the bulk fluid meets or exceeds the saturation levels [113]. The third species is
pyrite, which is associated with the form at high hydrogen sulphide partial pressure
[24].
Figure 6-7 shows that iron carbonate and iron carbide formed on the surface
after 2.5 hours sweet pre-corrosion at 50°C, 1% NaCl. After the specimen was
transferred to the sour vessel, an iron sulphide film starts forming on top of the
existing iron carbonate and iron carbide. It is likely that the iron sulphide was formed
by precipitation from the solution and transformation of the iron carbonate layers.
Figure 6-15 to Figure 6-17 show that the morphology of the sour specimens is
different at high temperatures and low temperatures. At higher temperatures the
solubility of the iron sulphide increases but the solubility of the iron carbonates
decreases [122]. At 90°C the morphology of the films present in the three difference
layers is shown in Figure 10-4. The first layer is the existing iron mixed iron
carbonate and iron carbide film formed in the pre-corrosion. The second layer is a
very thin iron sulphide film, which is likely to be mackinawite formation as a result of
the direct reaction between the hydrogen sulphide and the steel surface. The third
layer of iron sulphide will form due to the iron precipitation process and the type of
iron sulphide that forms on this layer will depend on the kinetics of the process. For
the 90°C specimen, the iron sulphide layer is more likely to be mackinawite due to the
EDX results, as shown in Table 10-1. Interestingly the XPS results in Table 6-5 also
indicate that the Fe 2P3/2 spectrum detects a strong peak of iron sulphide and weak
peak of iron carbide but not an iron carbonate peak. However, the CIs spectrum
indicates a weak peak of iron carbonate on the surface.
180
...... Iru' l C "rb{Jn d ~ ~
• ror C3r e
i)
Iron Sulphid e
sweet preecorrosion ~ (SeCCl 'ld L:=l)'er)
(After 2.5 hour) ...../ ror S, J rhlr.e
.---- ....... IF lr~ t L aYBr )
.... ............... ron Carbona:e
ii)
.-.-
... . rOl' C d r bc ~
• MJleri31
Later stage sour corrosion

Figure 10-4: Film formation in sour environments at 90 0 e
Temp. First layer Second layer Third layer

C% 5.2 8.6 7.4
0 % 4.2 25.4 28.9
S% 0 12.7 1l.2
Fe % 90.5 47.9 47.6
Table 10-1 : EDX on the sour fIlm at 90 0 e
At 15°e the morphology of the films also pre sents three different layers, as
shown in Figure 10-4. Howeve r, the third layer morphol ogy is changing due to the
kinetic s of the film form ation changing at low temperature. The fir st laye r is the same,
consisting of the existing mix of iron carbonate and iron carbide film from the pre-
corrosion . The second layer is mo st likel y to be the sam e thin macki nawite fi lm from
the direct reaction proce ss , which indicate s that thi s process is not influenced by
te mperature , as shown in Table 10-2. The third layer morphology , whi ch has a very
low sulphur content and very high oxygen content most likely indicates the form ati on
of iron carbona te film on the surface. Interestingly the XPS Fe 2P 3/2 spectrum results
in T able 6-5 also indicate a strong peak of iron carbonate and iron sulphide on the
surface . Thi s is considered to be due to the lower the tempe rature the lowe r the
181
solubility of the hydrogen sulphide and the carbonate acids have a higher solubility
resulting in the formation of iron carbonate.

C% 5.2 9.3 5.4
0% 4.2 21.7 34.9
S% 0 13.6 1.41
Fe % 90.5 48.8 56.8
Table 10-2: EDX analysIs on the sour film at 15°C
The third sour specimen that emerged at 15°C during starting and increased
the temperature during experiment to 90°C shows that the film content is more likely
to be influenced by the lower temperature morphology, as shown in Table 10-3. This
is supported by the SEM image in Figure 6.16. Figure 6.17 shows a small difference
in film morphology. As the third layer morphology has very low sulphur content and
very high oxygen content it most likely indicates the formation of iron carbonate film
on the surface. However, the second layer film also has a low sulphur content but
higher iron content, which is probably because the second layer film does not form a
cross the entire surface thereby exposing the pre-corrosion film and iron carbide
phase. This is attributed to the temperature change increasing the kinetic energy of the
iron precipitation and forming iron carbonate and iron sulphide due to the rapid
kinetic process.
C% 5.2 5.7 3.5
0% 4.2 17.9 35.1
S% 0 1.5 0.4
Fe % 90.5 68.0 59.6
Table 10-3: EDX on the film at 15°C and to 90°C

182
10.3 Sweet film breakdown and pit initiation

The iron carbonate film damage and film re-growth on the steel surface may
be one of the ways to initiate and propagate localized corrosion [53, 55]. It is
suggested that the water chemistry, with respect to Fe 2+ supersaturation, pH,
temperature and sodium chloride concentration, influences the film dissolution and
film breakdown process [55]. The specimen was immersed for 2 hours at 80°C and in
10% NaCI with saturated CO 2 to form a semi-protective film on the steel surface.
Higher concentrations of sodium chloride lead to more chloride ions, which stimulate
metal dissolution, especially at any particular point that is favourable for pitting
initiation [3]. Han et al. also show that higher localized attack was obtained in higher
NaCI concentrations [50]. After 2 hours, a mixed iron carbonate and iron carbide film
was formed with a corrosion rate around 3.5 mm/yr. Then the solution of the pH was
adjusted to 5.65 to reduce the solubility of Fe 2+, which corresponded to higher
supersaturation, and, therefore, accelerated the precipitation of iron carbonate. This
contributed to lowering the corrosion rate to 1.75 mm/yr [5]. During this period more
compact iron carbonate film formed on top of the mixed iron carbonate and iron
carbide film, as shown in Figure 7-2.
After 4 hours the 1000ppm FeCl 2 was added to the solution to achieve a high
concentration of Fe 2+ and increase the supersaturation of iron carbonate on the
surface. The corrosion rate dropped to the range of 0.75 mm/yr, because the high
supersaturation of Fe 2+ was able to heal the damage to the iron carbonate film by re-
growth of a new film layer on top of the existing iron carbonate and iron carbide. The
pit propagation rate slowed after the iron carbonate film actively grew a cross the
surface until 100 hours and covered around the pit area and partially covered the pits.
There is no significant change in pit diameter and iron carbonate film growth between
100 hours and 150 hours. It is interesting to observe the results from the in-situ
camera observation in Figure 7-3 on pit initiation after 5 hours at the uncorroded spot
area, which propagated to 30llm in pit mouth diameter after 8 hours. Observation by
the in-situ camera shows that the pit diameter growth is active in the first 3 hours after
initiation and then the pit diameter propagation rate slows and stops at 10 hours, as
shown in Figure 7-4. Figure 7-5 shows the SEM image of iron carbonate film on the
surface after 150 hours. Some damage to the surface is apparent in which the film
183
leaves footprints of iron carbonate crystals. However, the film protectiveness in this
case was not as low as 0.1 mmlyr, as reported in the literature, because the pH yalue
at 5.65 affected the adherence and sealing porosity [5, 55]. Han et a1. also showed that
the solubility of FeC0 3 is at the saturation line between supersaturation and
undersaturation at pH 5.65, 80°C and Fe 2+ concentration at 20ppm [50]. In this film
condition iron carbide is still left behind and provides local acidification, which
facilitates galvanic corrosion, and, hence, promotes initiation and propagation of
pitting. The structure of the mixed film plays an important role between the formation
and breakdown of the protective film, which leads to localised attack. The pits
initiating beneath the porous corrosion film will propagate into larger pits and the
remaining corrosion film on top will completely fill the pit or be removed stepwise by
flow, as shown in Figure 7-6 [55, 62].
Figure 7-11 in the results chapter shows that the pit depth measurements for
the 6-hour test to 70-hour test indicated nonlinear growth. The corrosion rate reduces
to 0.25 mmlyr after 6 hours and increases to around 1.25 mmly between 30 hours and
70 hours. This corrosion rate is supported by Nesic et a1. who predicted a corrosion
rate of 1.6 mmlyr after 30 hours in 250ppm of FeCh, pH 5.8 at 80°C [20]. It was very
interesting to discover that after 72 hours the corrosion rate dropped to 0.75 mmlyr
and remained constant until the end of the experiments at 150 hours. The corrosion
rate in the first 72 hours fluctuated due to the build up of the protective film and the
passivation and repassivation process that takes place on the surface. It was very
interesting to observe that the measured pitting depth indicated that the nonlinear
growth between 30 hours and 70 hours could be due to the film build up process
taking place, which promotes pitting initiation, reduces the pit propagation process
and leads to corrosion rate fluctuation [194, 195]. This is supported by Cheng et aI.,
who observed that the pit initiation stage could be indicated by the current fluctuation
due to the kinetics of pit growth and repassivation of the internal surface within the pit
and new deposit forming over the pit mouth [195]. This is also supported by Han et a1.
who indicate that localized corrosion is not propagated due to the scale formation
taking place [55]. Schmitt et a1. also show that the film thickness grew approximately
60~m after 50 hours and the film thickness did not change until 190 hours [62]. After
72 hours the pit depth obtained increased overtime until 150 hours and the corrosion
rate is constant at 0.75 mmlyr. The magnitude of pitting is established according to
184
the three maxImum pit depths for each set because it represents the worst-case
scenario for pitting corrosion, which leads to pipeline failure. Tests with a duration of
120 hours and 150 hours were run in triplicate to better establish the trends that could
differentiate inhibitor performance at various concentrations at a later stage. The pit
depth difference between the maximum pit and average pit at 150 hours is around
20~m, however, the average pit depth and maximum pit depth establish a good trend
for the pit propagation overtime. The measured pitting depth shows that the maximum
pit depth obtained after 150 hours is 73~m and the average pit depth obtained is
53~m. The replicate pit depth is difficult to obtain, as the pitting mechanism beneath
the protective corrosion layer involves the galvanic coupling between the steel and the
Fe3C left under the film, which force of acidification process and affects the local pH
[29].
Figure 7-6 shows that the cross-section morphology of the film consists of a
dark grey region, which is Fe3C that is in contact with the steel surface, and a whitish
flakes type film, which is FeC0 3 scattered and partially fills the film. A very thin
layer of whitish film, which is FeC0 3 , is also present in the outer layer of the film and
isolates the total film from the water solution. Precipitation of FeC0 3 at the outer layer
locally isolates the Fe3C from the solution and reduces the porosity of the corrosion
layer and causes an overall decrease in the corrosion rate, as shown in Figure 10-5.
This leads to the formation of a protective film and explains the phenomena of the
constant corrosion rate and constant film thickness between 72 hours and 150 hours.
A possible explanation for pitting propagation between 70 hours and 150 hours is due
to the FeC0 3 outer film layer isolating any disturbance in the local balance between
the respective anodic and cathodic reaction. This eventually leads to possible local
2
depletion in HCO; or a decrease in the local solubility of Fe + and enhances localised
reaction towards propagation activity. The argument has a good agreement with Han
et aI., who demonstrated that when iron carbonate is near the saturation level it will
create a favourable condition for localised corrosion propagation [55]. This is
supported by Jovancicevic et ai. observed that potential stabilization is an indication
of pit stable growth [196].
185
.. Iron Carbonate
.. --.. Iron Carbon ate
.. Iron Carbide
Material

(After 120 hours)
Figure 10-5 : FeC0 3 at the outer layer locall y isolating the Fe3C from the soluti on
The pitting growth mechani sm over time is shown in Figure 10-6. The
mechani sm is divided into three different zones. Zone 1, shaded green, represe nts the
fi lm breakdown stage. During this stage , depending on the operatin g conditi on, the
formation of mixed iron carbonate and iron carbide film s creates a favo urable
condition for pitting to initiate [3] .
-Film -Pits
breakdowns -Pits
initiation
-General -Pits propagation -Pits
-Film -Pits
corrosion initiation -Semi pro paga tion
formation in itiation
-Favourable -Film protective -Pits merging
-Film -Film
condition formation film
breakdowns formation
60 ~- 4
45
··----1~I _ __ _~/_____ _~/_ _____~r--_
-----7
--7_---_
'-'_
'-'_
"-_
"-_
""_
-'_
-"_ ..7
....~ _. -_--_. ·_. . ·_-.-_---·_----·~·-~....~...._-·---+ 3 i
1I
E : I / / 1 / / E
-3 !I / / 1/ / ~
.c 30 +.4~~----,-------7---------~~--------~~~--------~--+ 2 e c
'& o
v
a
~
15
g
0: o
U
0
0 20 40 60 80 100 120 140
Time (hours)
~ Ave Pit Depth -+- Corrosion rate
Figure 10-6: Schematic repre sentation of pitting gro wth mec hani sm ove r time fo r X65
2
carbon steel in C02 saturated , 10% N aCI brine at 80°C , pH 5.65 and 1000ppm Fe +
During thi s stage , the corrO SIon dam age is dominated by general COlTOS lon .
When the favourabl e conditi on is ac hi eved , the pit initi ation stage will start, whic h is
represented by the yell ow zo ne _ Durin g thi s stage , th e film breakdown proce ss wi ll
continue due to the kine ti cs of pit initi ati on and re pass ivatio n of the intemal sUlface
w ithin th e pit and new depo sit s forming over the pi t mouth [1 95]. Thi s process will
186
cause a fluctuation in the corrosion rate [194, 195]. When the semi-protective film is
fully formed, the propagation stage will start, which is represented by the red zone. In
this zone the corrosion rate is consistent but the pit will propagate deeper and larger
over time [196].
10.4 Sour pitting behaviour

Under sour conditions, iron sulphide will precipitate on the metal surface
reducing the general corrosion rate [126]. However, if iron sulphide is not fully
covered the metal or iron sulphide film breaks down and there will be exposed anodic
sites on the metal [126]. This will lead to a large cathodic area in the iron sulphide
film, and, consequently, small anodes at breakdown locations, which will result in
accelerated corrosion that may grow into pits or could also appear as a uniform attack
with a rough surface [126, 130]. Figure 7-7 in the results chapter shows that pH has a
significant effect in reducing the corrosion rate, which is also reported by Sun et al.
[110]. Stable iron sulphide is more likely to form at pH 5.65 and as a result decreases
the corrosion rate.
2
Increasing the Fe 2+ concentration by adding 1000ppm of Fe + shows a contrary
reaction by drastically increasing the corrosion rate to 16 mmlyr. This might be
because additional Fe 2+ ions in the solution have a direct reaction with the H:~S gas
and are unable to form a protective iron sulphide film. However, there is no
significant effect of pH and Fe 2+ concentration in terms of pitting depth measurement.
The main effects for pitting in these experiments were the influence of high chloride
concentrations at 10% NaCI and high temperatures of 80°C. This is supported by Sun
et al. who suggested that higher chloride concentrations might impair the iron
sulphide scale consistency, and, consequently, cause pitting corrosion [110].
Kavarekval et al. also observed that higher temperature environments increase the
pitting corrosion attack [132]. Figure 7-12 shows that increasing the exposure time
generates more severe localized corrosion and deeper pits. After 4 hours exposure
time the maximum pit depth recorded was around 10.211m with a corrosion rate at 0.4
mmlyr.
187
After 96 hours the maXImum pit depth increased to around 3 1flm and the
average of 3 maximum pit depth s is 29 .8 flm with a fin al corrosion rate rec orde d at
0 .3 mmlyr. These results are supported by Ka varek val et aI. , who reported th at the pit
depth increases over time and obtained a maximum pit depth of 25 ~m with a fin al
corrosion rate of 0.33 mm/yr after 96 hours in 0. 1% NaCI, 60°C, 0 .02 bar H 2S and 1
bar CO2 [1 32]. Sun et al. reported that pitting in a sour environment is a non-linear
process and that the film passivation and repassivation ac ti vity will influence the pit
propagation rate [129]. Ka varekval et al. reported that the pit passi vation process
seems to be dependent on the corrosion product precipitating within the pit s [132] .
Figure 7-9 show s that the iron in the film layer consists of two irregular layers of
crystals in which the top layer poorly adhered to the surface and formed pit clu sters
[4, 130] . Kavarekval reported that the pit clu ster was covered wi th numerous smaller
pits and clu sters [130] . Thi s indicates that the pitting event take s place at the pit
cluster and sustains an active pit environment at the pit mouth to propagate further
and resulting consequential pit depth [133]. Thi s is also supported by Kvarekval , by a
SEM cross-section of the pit, show s that it was covered by a FeS corrosion film
probably mackinawite [132]. Fi gure 10-7 shows the pit growth mech ani sm of sour
pitting in sour environments . Thi s show s that the pit will initiate at the film
breakdown site and initiate the pits. Then , the film breakdown location wi ll become
small anodes and the iron sulphide film will be a large cathode, which wi ll result in
accelerated corrosion that may grow into pits [1 26, 130].
- FeS formation
- Film breakdown Iron Sulph ide
c=J.... IDDDDD~+:~M","'
Uncorroded After 1 hours
(as polished)
- FeS formation
- FeS formation
_ Pit initiation .... Iron Sulphide ". - Pit propagatio n
,A'"
After 4 hours After 96 hours
Figure 10-7 : Sc hemati c repre sentati on of pitting growth mechani sm over tim e for X65
carbon steel in 10% H 2S 90% CO 2 , 10% NaCl brine at 80°C and pH 5.65
188
10.5 Inhibition of pitting propagation by phosphate esters in sweet

environment
Phosphate ester compounds are commonly used as an active component in the
corrosion inhibitor due to its adsorption characteristics and effectiveness as an anodic
corrosion inhibitor [98, 106]. Phosphate esters, in general, are used to inhibit general
corrosion in the oil and gas environment, however, the synergistic effect of phosphate
ester with other inhibitors have been suggested to reduce localized corrosion [106].
Most work on inhibitors has been carried out to study the inhibiting effect on the
general corrosion or pitting corrosion starting from the initial stage of corrosion.
However, in this present work, phosphate ester was used to study the effect on pitting
propagation after 120 hours pre-corrosion. Figure 7-15, in the results chapter, shows
that phosphate ester was added into the test vessel at 120 hours to stop pitting
propagation. The inhibitor resulted in a small increase in the corrosion rate at lower
concentrations between 10ppm to 50ppm but did not show any significant effect at
higher inhibitor concentrations. This corresponds with the suggestion that the
interaction between the phosphate ester and Fe 2+ raises the corrosion rate, as the
concentration of the inhibitor appears to be under the minimum value required to be
adsorbed at the surface. Wong et al. shows that phosphate ester lowers the corrosion
rate by preventing the growth of iron carbonate film when the concentration of
phosphate ester is at least 25ppm [98]. Alink et al. and Wong et al. showed that
2
phosphate ester forms a stronger complex with Fe + to form iron phosphate, which
prevents the formation of iron carbonate layer and provides better protection to reduce
further attack if applied above the minimum concentration required [98, 106].
In this test condition, the iron carbonate layer had already formed after 120
hours and adding phosphate ester at this time further affected the rate of precipitation
of iron carbonate film, which affects the adsorption mechanism onto the existing film.
At lower than minimum concentrations of phosphate ester, it is postulated to slow
2
down the precipitation rate of iron carbonate and form a weak complex with Fe +
resulting in a mixed reaction with less adsorption to the existing film, as shown in
Figure 10-8. These types of film possibly change the film structure to increase the
porosity by reducing the iron carbonate crystal structure and lead to loss of protection
with consequent increase in the corrosion rate [98].
189
However, if the required amount of phosphate ester is applied. it will form a

stronger complex with Fe 2+ and preve nt further formation of iron carbonate. The
corrosion rate doe s not change, which could be because the exi sting iron carbonate
film structure is still unchanged and provides the same corrosion protection. The
literature show s that when phosphate ester is added after a long pre-corrosion time it
may not have any effect on the corrosion rate due to the cementite layer on the sUlface
of the steel [91 , 98 , 192] . It is interesting to observe that Akbar et al. also show that
the inhibitor does not reduce the corrosion rate in the erosion corrosion te st after pre-
corrosion [197]. However, when pho sphate ester is added at the beginning of the test,
it shows a reduction in the corrosion rate [98] . Thi s could be due to the pho sphate
2
ester mechanism , which forms a complex with Fe + and is tran sported through the
porous film where it reacts with Fe 2+ and the base metal. This is supported by
Dougherty, who shows that above the threshold concentration, the inhibitor is
transported to the metal surface for inhibition [198] . Further in vestigation wo uld have
2
to be carried out to study the product formed from complex Fe + and phosphate ester
after long pre-corrosion.
...... .... .....~ Iron Carbonate

.-.- ~ Iron Carbonate
.. Iron Carbide
Material
Figure 10-8: Effect of underdose of phosphate ester
Figure 7-18 in the results chapter shows that phosphate ester is able to
significantly decrease and stop pitting propagation at doses above the minimum
concentration required . The data show that the inhibitor works with effective
performance after 2Sppm. The pit depth shows a slight increase at 300ppm of
inhibitor, which is po stulated to be due to the higher inhibitor concentration beyond
the critical va lue of the inhibitor concentration. Figure 10-9 compares the average pit
depth and average general COlTosion rate with the concentration profile and shows the
phosphate ester mec hani sm on the concentration profi le. The data show that after
7Sppm the ave rage pit depth and final corrosion rate shows the same trend .
190
-Consistence general corrosion

-Pits propagation stage
• ........ Pre-corros ion fi lm

-Increase general
-No effect to
corrosion
general corrosion
-Not effect to Pre-corrosion -Control
localised corrosion film with pits localised corrosion
' - - _ - = - _ - - - ' .. . . .. .. . . ...... in h i b ito r ...................f--...----~

Underdose L.....,;-.=--,,..--_.....J
Concentration
~ - 4
~ 45 / ~
'-
E
7
>,
-3 ">
c:
...c: E
a.
<l)
30 2 OJ
0 ;;;
~
0: c:
0
IS v:
9
c
0
U
0 0
0 SO 100 IS O 200 250 300
Inhibito r Concentration (ppm )
~ PitDepth - Corrosion ra te
Figure 10-9: Schematic representation of phosphate ester mechani sm on concentrati on

profile on X65 carbon steel in CO 2 saturated 10% NaCl, pH 5.65 , 1000ppm Fe 2+ , at
80°C
It is interesting that, at 10ppm, the corrosion rate is still at a lower rate but
produces a deep pit, which indicates that the formation of iron carbonate is still taking
place on the surface and the inhibitor concentration still appears to be under the
minimum value required . During thi s stage the inhibitor might be insuffici ent to
tran sport to the metal surface to provide protection and the concentration is too low to
affect the pre-corrosion layer [197 , 198]. As the inhibitor concentrati on increases
from 25ppm and 50ppm , it indicates the transiti on concentrations , whi ch explain the
slow rate of formation of iron carbonate due to the inhibitor transported to the metal
surface . The se concentrati ons also start forming a stronger comp lex betwee n the
2
inhibitor with Fe + by red ucing the pitting propagation . The inhibi tor work
191
effectively after 75ppm by reducing the final pit depth and does not increase the
corrosion rate. During this stage the inhibitor is sufficient to transport to the metal
surface to perform localised protection. It is interesting to note the relation between
the pitting propagation and complexation of Fe 2+ by phosphate ester after pre-
corrosion. It is postulated that the phosphate ester is transported to the metal surface
through the pre-corrosion layer to perform complexes with Fe 2+ to form iron
phosphate and is absorbed at the pitting site, which reduces the iron dissolution and
prevents further pitting propagation. This is supported by 10vancicevic et aI., who
observed that anodic inhibitors strengthen the protective film by adsorption thereby
reducing iron dissolution and lowering localised corrosion [199]. However, the
adsorption behaviour of phosphate ester on the pit sites leaves the long pre-corrosion
film without protection and is unable to control the general corrosion rate after long
pre-corrosIOn.
10.6 Inhibition of pitting propagation by imidazoline in sweet

environment
Extensive use of imidazoline corrosion inhibitors in oilfield applications to
protect the carbon steel from general corrosion have generally been successful,
however, the mechanisms of inhibition, especially with pitting, are not widely
understood [42, 98, 104, 105]. In this set of experiments, imidazoline was used to
study the effect on pitting propagation after 120 hours pre-corrosion. After 120 hours
pre-corrosion, a mixed iron carbonate and iron carbide film had already formed and
pitting had already been initiated and propagated. The effect of irnidazoline was
observed in terms of the corrosion rate and final pitting depth at the end of the
experiments at 150 hours. Figure 7-17 in the results chapter shows a significant
increase in the corrosion rate after 10ppm inhibitors were applied, however, no
significant change in corrosion rate was observed for 25ppm, 50ppm, 75ppm and
100ppm.
Nevertheless, a slight decrease in corrosion rate was observed at 200ppm and

300ppm concentrations. This result is supported by the literature, which shows that
imidazoline reduces the corrosion rate after a long period of pre-corrosion [65, 91,
98]. The results suggest that imidazoline interaction with iron carbonate film and
192
forming the imidazoline monol ayer go vern s the mechani sm to reduce the cOITosion
rate [6S , 98] . At 10ppm inhibitor concentration, the cOITosion rate increased
significantly after the inhibitor was added and the improvement towards the end of the
test shows that the interaction between the inhibitor, Fe 2+, and the exi sting iron
carbonate film on the surface. Wong et aI. and Chokshi et aI. reported th at in the
presence of iron carbonate film , imidazoline inhibitor will interac t with Fe 2+ and
create an adsorbing film to reduce the cOITo sion rate [6S , 98]. Wong et aI. reported
that at concentrations above 2Sppm , imidazoline prevents the growth of iron
carbonate film on the surface, however, at Sppm and 10ppm concentrations the
formation of iron carbonate film continues to grow , however, it also reduces the
corrosion rate [98] .
In this test condition the inhibitor possibly tries to form a monola yer on the
existing iron carbonate scale. However, due to the lower inhibitor concentrati on, the
reaction mechanism with Fe 2+ is weaker compared to the precipitation of the iron
carbonate film resulting in a mixed film between the iron carbonate and imidazo line
film , which reduced the corrosion towards the end of the test [6S , 98 , lOS] . At
concentrations between 2Sppm and 200ppm , it is suggested that the inhibitor form s a
monolayer on the existing iron carbonate film and prevents further formation of an
iron carbonate film , as shown in Figure 10-10 .
...... _..... --... .. Imidazolines film

~:~---=::- . ----- .. - .. Iron Carbonate
. ...... -...... --............ Iron Carbonate
.. Iron Carbide
Material
Figure 10-10: Imidazoline film
However, due to the thicker pre-coITosion film on the surface , no signi ficant
decrease in the corrosion rate was observed. Thi s is supported by Chokshi et aI. , who
observed that the film porosit y was very similar after adding inhibitor or with out
inhibitor after 47 hours pre-corrosion time . 10vanci cevic et aI. shows that at hi gher
inhibitor concentrati ons , the imidazo line fi lm will form a thicker film with the
193
prese nce of larger micelles on the surface and lead to the forma tion of a bil aye r [6 5.
105 ] . Thi s ex pl ain s that wi th 200ppm and 300ppm inhibitor the imidazoline fonTI s a
bil aye r film and a thicker film resulting in a slight reduction in the con-osion rate .
Fi gure 7 -20 in the results chapter shows that imidozoli ne was able to decrease
and stop pitting propagation even at lower concentrations. Thi s is supported by
10vancicevic et aI. , who observed that the imidazo line monolayer film formed a
barri er to water and chloride ingress thereby protecting the surface [1 05]. In this
work , it sho ws that the imidazoline film not only protec ts the surface from general
corrosion but also from further pitting propagati on after long pre-con-osion, as shown
in Figure 10-11 .
-Consistence general corrosion

-Pits propagation stage
.--------- Pre-corrosion film
-Increase general -Control

corrosion general corrosion
-Control localised Pre-corrosion -Control
corrosio n film with pits localised corrosion
--- ----- --- --------- in h ibitor ·,---------·----- + ·1,.·····

~~~~--~ ~~~~--~
ive
Concentration Concentration
T 2
l /
45 ~~~J.~----------------------------);?'
~ --~L-------------~
/ ...
»
E
E
0
':ii
0:::
c:
c
-r.
e
I...
0
U
0
o 50 100 150 200 250 300
In hi bitor Concentratio n (pp m)
~ Pi t Depth - Corrosion rate
F igure 10-11 : Sc hematic represe ntati on of irnidazoline mec hanism on concentration

1+
profile on X6S carbon steel in CO 2 saturated 10 % NaCl , pH 5.65. 1000ppm Fe- . at
80°C
194
At an effective concentration, imidazoline adsorbs on the pre-corrosion film

2
and Fe + on or near the metal surface. This is supported by 10vancicevic et al.. who
indicate that cathodic inhibitors adsorb onto the iron carbonate film thereby
interfering with the proton reduction [199]. This is also supported by Wong et ai. and
Ramachandran et aI., who observed that imidazoline interacts with Fe 2+ and creates an
adsorbing film on or near the metal surface [98, 200]. It is interesting to observe that
at higher imidazoline concentrations, the final pit depth increases slightly even though
the corrosion rate decreases. Chokshi et al. reported that the imidazoline film reduces
the precipitation and supersaturation of iron carbonate to reduce the corrosion rate,
however, this leads to slightly more acidic conditions on the metal surface [65]. It is
postulated that at higher concentrations, a thicker bilayer film forms there by
providing protection and reducing the corrosion rate, however, it leads to a more
acidic environment at the metal surface, which results in slight pitting propagation
[65, 105]. An alternative postulation could be that the thicker bilayer film created by
the inhibitor film creates an under film localized environment that lead a favourable
pitting condition. It is interesting to note that the imidazoline concentration controls
the thickness of the imidazoline film layer and that thickness influences the protection
mechanism to reduce the corrosion and localized attack. At lower imidazoline
concentrations, the underdose effect slightly increases the corrosion rate but still
provides a localised corrosion protection after long pre-corrosion. This is postulated to
be due to the slow transport of imidazoline through the thicker pre-corrosion film to
adsorb on the metal surface thereby causing the slow absorption of imidazoline on the
pre-corrosion film.
_____1f)L1
. __________ mog"" !IIg.. • . . . .
~~~·~~~y·~ ~c •
t •
I
js
-
.......I g -----
condition
Artificial pits made from microhardness indentation were developed with the
aim of conducting preliminary laboratory testing on inhibitor assessment prior to a
field trial. This artificial pit design simulated any indentation or small defect in the
pipeline during the installation stage and operational stage that normally becomes a
hot spot for pitting attack when the favourable conditions take place. This is supported
by Chu et aI., who show that pits are more likely to initiate at metallurgical
discontinuities on the surface, such as grain boundaries, pearlitic colonies and banded
195
phases in the steel [104]. Laycock et al. also showed that pits are likely to initiate at
occluded geometries because both ohmic and diffusional resistance are higher at these
sites, which create a favourable condition for pitting [7]. Comparing these artificial
pits with Turnbull et aL' s "pencil pit" and Nesic et aL' s "artificial pits", this artificial
pit propagates naturally from the autocatalytic nature of pitting and growing in the
direction of gravity compared to the existing artificial pit design by galvanic
mechanisms that separate the anode and cathode [50,69].
In this study it is difficult to monitor the growth of the pitting propagation

either laterally or in depth direction due the extreme experimental condition and the
nature of carbon steel pitting covering the pits with corrosion deposit. A long
experiment time and higher Fe 2+ concentration, creates a challenging environment to
obtain good visibility on the pit surface. However, this in-situ observation technique is
able to monitor the growth of the film on the surface of the pits and the reaction of the
inhibitor with the film at the pit sites. This technique will be a powerful technique to
observe the carbon steel pitting initiation process in shorter duration tests and observe
the inhibitor effect on the pitting initiation. This technique is also very good for
observing the pitting behaviour in stainless steel and other alloy materials. Comparing
this in-situ technique with other similar observation techniques in the literature, this
technique could perform at higher temperatures of up to 80°C in one single cell with a
glass window without the need for a separate glass window unit in the corrosion loop
[47, 78, 145, 146]. Moreover, by using this in-situ observation technique it is also
possible to observe the early stages of iron sulphide film formation in sour conditions.
Due to the blackish colour of the iron sulphide film, it is possible to observe and
determine the effect of sour gas after sweet pre-corrosion using this technique.
Figure 8-1, in the results chapter, shows the formation of iron carbonate film
repeating the same procedure from the previous Chapter 7 tests to reduce the
corrosion rate before a potentiostatic current is applied at 100m V from OCP for 20
hours to initiate and propagate the pit. The average pit depth for the artificial pit from
the three blank tests is 46.8~m and for the natural pit depth is 67.7~m. Comparing the
average natural pit obtained from the potentiostatic method procedure with the natural
pit growth procedure from the previous experiment shows that this method accelerates
the pitting propagation process and reduces the experiment time by 859c or 6 days but
196
still obtain s the de sired pit depth . There was about 20 ~m difference in the average
final pit de pth be twee n the artificial pit and natural pit on the sUIface . however. this
was due to the extreme te sting environment and the nature of pitting itse lf. One of the
main benefits of the artificial pit technique is that the in-situ camera can monitor the
surface area of the artificial pit from the early stage of the experiment until the end of
the experiment. Figure 10-12 show s the in-situ condition of the artificial pit at the
start of the experiment and before the end of the experiment. Thi s shows that the film
grows on the film as well as in side the artificial pit. Thi s is supported by FTIR
analysis in Figure 8-17 , which identifies the film as iron carbonate film . However, the
absorption of iron carbonate film on the artificial pit could be weaker due to the
geometry and simulated film breakdown and lead to artificial pit propagation .
Figure 10-12: In- situ artificial pit surface at stal1 of the test and after 24 hours in C02
2
saturated 10% NaCI , pH 5.65 , 1000ppm Fe + , at 80°C
Using the in-situ observation technique it is not possible to monitor the growth
of the artificial pits in lateral and depth direction because the corrosion product
constituted at the edge of the pit mouth covering the cementite layer left behind and
the pit propagates beneath the original corrosion film on top of the edge of the pit
mouth [47, 194, 195] . Figure 10-13 show s the artifici al pits growth mechan ism based
on the in-situ observation findings .
The literature shows that pitting initiation ge nera lly occ urs at occ luded
geometry sites on the surface [7, 104] . Creating artificia l pits simula tes a hot spot
w here the pit s w ill grow . Iimura et a!. observed that the pH inside the artificial pits
197
dropped due to the chl oride ions bein g concentrated w ithin the pi t [ 194 ]. Cheng et al.
o bserved that chl oride ion s mi grate into the inc lu sio n site and create an occ luded
cavity, which cause s di ssoluti o n of the metal cati ons [195 ]. T herefore, the artificial pit
gro wth is due to the concentration of cr inside the artificial pits, which conti nues to
propagate w hen the deposit fil1 s the artificial pits and creates a fa vourable co nditi on
for pitt ing grow th . It is very interesting to compare the mechanism of the arti fic ial pit
and the natural pit in Figure 10-6 . A lthough both pits ex perience simil ar conditi ons
they propagate usin g two differe nt electroc he mi cal technique s. Thi s shows th at the
artificial pit u sing the accelerated potentiostatic technique is able to simul ate the
natural pitting grow th technique in a more time effi cient way .
- Unprotective films - Sem i-protective fi lms

- GI- concentrate at - CI- concentrate at
Artificial Pit artificial pits artific ial pits
Material G
v ..·I ron Carbonate ". G
V
~... , mOC;i de ~
C=j
After 1.5 hours After 3 hours
Uncorroded
(10% NaGI) (1 0% NaGI , pH 5.65)
(as polished)
- Semi-protective films - Artificial pit

- Gr and Fe 2+ propagate
concentrate at artificial - Deposit fi ll the
pits artificial pit
0 0
~
._._ .. ,, ~ Iron Carbonate
Potentiostatic
.......... ~ Iron Ca rbide

(1 0% NaGI , pH 5.65 , 1000ppm (1 0% NaGI , pH 5.65 , 1000ppm
Fe 2+) Fe 2 +)
F igure 10- 13 : Artifici al pit growth mec hani sm in CO 2 saturated 10% NaCI , pH 5.65 ,
1OOOppm Fe 2+ , at 80°C fo r 24 hours

198
10.8 The effect of phosphate ester on artificial pit growth under

sweet condition
Figure 8-3 from the results chapter shows that lower concentrations of
inhibitor result in higher current up to 80mA, however, when the inhibitor
concentration increases there is no significant difference in the current compared with
the blank specimens. It is interesting to compare the potentiostatic current behaviour
with linear polarization results from the long test in Chapter 7. Both tests show the
same trends with an increase in the corrosion current at lower concentrations and no
significant effect in terms of corrosion current at higher concentrations. Figure 8-13
shows the difference between the maximum and average pits that grow on the surface.
It shows that with a lower phosphate ester concentration, both the artificial and natural
pits propagate deeper than the blank specimens, however, when the concentration
increases the propagation rate slows down resulting in a reduction of pitting depth. It
is interesting to note that the difference in pit depth between the artificial pit and
natural pit reduce when the phosphate ester concentration increases, which indicates
that both pits corresponded in the same way towards inhibitor performance. These
similar trends indicate that the pitting activities and the reaction with the inhibitor are
comparable between the artificial pits and the natural pits. Comparing these results
with the previous long test results from Chapter 7 shows similar trends in terms of pit
depth corresponding to inhibitor concentrations.
At lower phosphate ester concentrations, pit propagation is significantly higher

than the blank test. It is postulated that less adsorption of the inhibitor molecules
within the pit sides results in the reduction of inhibitor performance and consequential
increase in the propagation activities [7]. An alternative postulation may be that at this
concentration it generates an interaction from various chemistries contained in the
inhibitor resulting in the nullification of the corrosion inhibitor [7]. It is interesting
that the in-situ camera shows that at lower inhibitor concentrations, the artificial pit
was covered by a black deposit and the FTIR analysis also indicated the absence of
inhibitor at the artificial pits. It is clear that the reason for the pit propagation was due
to the black deposit covering the pit and blocking the inhibitor from accessing the pit,
which generated a localized environment that favours pit propagation activity.
However, after the inhibitor concentration appears to be above the minimum value
199
required the propagatio n rate decreased becau se the inhibitor absorbed in the pit sites
and stopped the bl ack deposit covering up the pit there by avoiding the creati on of a
locali sed cell. T his is supported by the FTIR analys is, whic h indic ated the presence of
inhibitor at the pit sides . T he inhibitor molec ular was absorbed in the pit sides
resulting 1I1 the formati on of an inhibitor film at the pi t side s, which delayed the
propagation of the locali sed cell [7]. Figure 10- 14 shows the phosph ate es ter
mechani sm on the artificial pits. It shows that an effec tive concentration of phosphate
ester is attracted to Fe 2+ and the low pH sites inside the artificia l pits form iron
phosphate to provide protecti on against localised cOlTosion. Howe ver, at lower
concentrations an underdose effect is observed due to the fa ilure to transport to the pit
site and react with the pre-c olTosion product, which leads to the form ation of a black
deposit that cove rs the pits. Further investi gation would have to be calTied out to
study the black deposit product form ed at the pit sites during the underdose condi ti on .
-Semi protective film
eJ®
~
After 3.5 hours
pre-corrosion
-Inhibitor reaction cover -Inhibitor absorbed to
the pit sites pit sites
-Not control localised -Control localised
corrosion corrosion
~ ... . ..... Iron Ca rbonate .....

................... -- Iron Carbide ··.. ·.. ·········· -- ·····--····
" ." ,., Inhibitor ......
Underdose Effective
After 24 hours
Figure 10 -1 4 : Phosph ate ester mec hani sm in CO 2 saturated , 10O/C NaCI. pH 5.65 ,
1000ppm Fe 2+ , at 80°C for 24 hours

200
10.9 The effect of imidazoline on artificial pit growth under sweet

condition
Figure 8-5 from the results chapter shows that Imidazoline provides better
protection to reduce the applied current, as the inhibitor concentration increases,
which might be because the inhibitor protects the overall surface by forming a film of
imidozaline. It is interesting to compare the potentiostatic current behaviour with the
linear polarization results from the long test in Chapter 7. Both tests show the same
trend, which reduces the corrosion current as the inhibitor concentration increases,
which could be because the inhibitor forms a thicker film at higher concentrations.
Figure 10-16 shows the difference between the maximum and average pits that grow
on the surface. It shows that both artificial and natural pits propagate in the same
manner and propagate deeper at higher concentrations compared to the blank
specimens. This similar trend indicates that the pitting activities and the reaction with
the inhibitor are comparable between the artificial pits and natural pits, which
indicates that both pits corresponded in the same way towards inhibitor performance.
Comparing these results with the previous long test result from Chapter 7
shows a similar trend in terms of pit depth corresponding to inhibitor concentrations.
Both results show that the inhibitor reduces the pit propagation even at lower
concentrations; however, the artificial pit test shows a significant mcrease in pit
propagation rate at higher inhibitor concentrations compared to the slight increase in
the long test. It is postulated that this is due to the difference in pre-corrosion time
between the tests, in that the artificial pit only has 4 hours pre-corrosion test, which
corresponds to a thinner iron carbonate film. This means that at higher concentrations,
imidazoline could form a thicker film to form the barrier, which leads to more acidic
environments at the metal surface there by influencing the pit propagation. An
alternative postulation may be because at higher concentrations it generates an
overdose effect reaction within the inhibitor and Fe 2+ resulting in the nullification of
the corrosion inhibitor [7]. It is interesting that the in-situ camera shows that at higher
inhibitor concentrations, the artificial pit was covered by the black deposit and the
FTIR analysis also indicates that the absence of inhibitor at the artificial pits and the
film area. It is clear that the reason for the pit propagation was due to the black
deposit covering the pit and blocking the inhibitor from accessing the pit. which
20 1
ge nerates a locali zed enviro nment that fa vours pit propagati on ac ti vity. However. if
the inhibitor concentration is below the maxi mum values required , the inhibitor wi ll
not be absorbed on the surface and form an imidazoli ne film to provide protec ti on
from general corrosion attac k and locali sed corrosion attack . Thi s is supported by the
FTIR analysis, which indic ated the presence of inhibitor on the fi lm area and at the
pits site. The inhibitor molec ules were adsorbed on the surface re sultin g in inhibitor
fi lm formation thereby delaying the propagation of localised cell s [7]. Figure 10-15
show s the imidazoline mechanism on a11ificia l pit s. It shows that an effec ti ve
concentration of phosphate ester is attrac ted to Fe 2+ on or near the metal surface and
on the film . Imidazoline will form an imidazoline monolaye r, whi ch go ve rns the
mechanism and reduces the corrosion rate [65 , 98]. However, at highe r concentrations
an overdose effect is observed due to the thicker imidazoline film forming a barrier,
which leads to more acidic environments at the metal surface , thereby influenci ng pit
propagation .
-Semi protective film
e®
-Inhibitor reaction
~
After 3.5 hours
pre-corrosion -Inhibitor absorbed to
cover the film and corrosion film and the
the pit sites pit sites
-Not control localised -Control localised
corrosion corrosion
...... Inhibitor ......
___ ........._._........... Iron Carbonate ................................ :: .
.............................. Iron Carbide ......................
..... Inh ibitor .........
Overdose Effective
After 24 hours
Fiaure 10-15 : Imidazo line mechani sm in CO 2 saturated, 10% NaCI , pH 5.65 ,

b
1000pp m Fe 2+ , at 80°C for 24 hours

202
10.10 In-situ monitoring of artificial pit growth under sour condition

Artificial pit techniques with in-situ camera observation have been developed
for sour environments to evaluate pitting corrosion inhibitor. The design for artificial
pits in sour environments is similar with sweet environments using microhardness
indentation. The geometry of the artificial pit affects the stability of the iron sulphide
film and becomes a hot spot for film breakdown and pitting propagation [139, 141].
Marsh et al. used the artificial pit technique to evaluate inhibitor performance in a
sour environment by a pre-corrosion electrode coupled through an ammeter to a larger
electrode [141]. Figure 9-1 in the results chapter indicates that the formation of iron
sulphide provided a protective film on the surface by reducing the corrosion rate of 1
mrnIyr in the first 2.5 hours before the potentiosatic current was applied at lOOm V
form OCP for 20 hours to activate the artificial pit and propagate to the desired depth.
Due to the lower pH and high chloride concentration, the film that forms after 2.5
hours is semi protective, poorly adherent and easily removed, which could lead to a
pitting attack [135, 139, 141].
The in-situ camera shows in Figure 9-9 that after introducing the sour gas the
blackish film gradually deposited on the sample surface and after 1 hour, the film
grew over the artificial pit surface. FTIR analysis shows that the blackish film was
iron sulphide film consisting of mackinawite and pyrite. After 1 hour, the observation
through the glass wall showed that the solution turned black in colour, which could be
because of the dissolution from the iron sulphide film due to the low solubility in
water. After the 24-hour test, the average artificial pit depth was 31.61lm and the
average natural pit was 34.9Ilm; approximately a 2.71lm difference in depth. This
suggests that the average condition in the artificial pit and natural pit shows similar
behaviour in propagation stability; however, the maximum natural pit on the surface
reached 49.31lm due to the morphology of the iron sulphide film, which may be
subject to local breakdown. This could be because the propagation process over a
period of time is related to the diffusion characteristic associated with the pit depth;
however, the pit depth trend is similar [141].
20 3
Figure 10-16 show s the artificial pit growth mec hani sm in a so ur environ me nt
b ased on the in-situ observation fi ndings. It is intere sting to observe th at the arti fic ia l
pits in both the sweet and sour conditi on s start growth due to chl oride ion mi g rating
into artifi cial pits [195] . However, under sour condition s the quick form ati on of iro n
sulphide fills the artificial pit mouth within one hour. The propagati on mechani sm is
different between sweet and so ur pitting due to the conductive iron sulphide film . Due
to the artificial pit geometry, the films that form on top of the pit mouth are not stable
and lead to film breakdown . This will create a large cathodic area in the iron sulphide
film , and , consequently, small anodes at the breakdown locations, which wi ll res ult in
accelerated corrosion that may cause the artificial pits to grow [1 26, 130] . It is very
interesting to compare the mechani sm of the artificial pits and the natural pits in the
sour environment. Both pits have a similar propagatio n mechanism but use different
electrochemical techniques. This show s that the artific ial pits using the accelerated
po tentiostatic technique in a sour environment are ab le to simul ate the natural pitting
growth technique in a more time efficient way.
- FeS formation
- cr concentrate at
Artificial Pit artificial pits
... ~
Material .' Iron Sulfide
...... Iron Carbide
~
d Uncorroded After 1 hours

-~.
(as polished)
- FeS formation
~ ~~~n~~~~~~on........../ Iron Sulfide - Pit propagation
......Iron Carbide
~/ potenti;tatiC
Figure 10-16: Artificial pit growth mechani sm in 10% H 2S , 90 % C02 , 10% NaCI at
80°C for 24 hours

204
10.11 The effect of nonoxynol-6 phosphate on artificial pit growth

under sour conditions
Corrosion inhibitors are often used in sour environments to control general
and localised corrosion [141, 116]. Corrosion inhibitors are adsorbed in the iron
sulphide film and change the morphology and wettability of the film to provide
protection to the surface [139]. The active component in the inhibitor may reduce the
dissolution of scale into an aqueous environment or hinder the diffusion control led
growth of iron sulphide scale or prevent spilling of the scale surface [116].
Nonoxynol-6 phosphate inhibitor belongs to the phosphate ester inhibitor type group.
Figure 9-3 from the results chapter shows that inhibitors can reduce the corrosion rate
gradually even at lower concentrations. This is supported by Wang et al. who show
that lSppm concentration of polyethoxylate alkyl phenol could provide protection to
reduce the corrosion rate [139]. The performance of the inhibitor to reduce the
corrosion rate increases as the inhibitor concentration increases; however, the pit
depth analysis in Figure 9-13 shows a contradictory effect. The difference between
the average and maximum pit depth is about 20~m for the natural pit at 2Sppm but as
the concentration increased to 100ppm and 200ppm the difference decreased
significantly. This suggests that the inhibitor reaction was not very stable below the
minimum concentration desired to mitigate pitting attack. The inhibitor performs at an
effective concentration at 100ppm and it is interesting that the FTIR found the
inhibitor element on the film area and pit area. The in-situ camera observation shows
that the inhibitor prevents the growth of iron sulphide film on the surface and from the
FTIR analysis it suggests that the inhibitor creates an inhibitor monolayer to prevent
general corrosion and pitting corrosion.
However, at 200ppm inhibitor concentration, Figure 10-17 shows that the

inhibitor reduces the general corrosion but promotes the propagation of pitting. It is
postulated that an overdose occurs at a concentration of 200ppm, which forms a
thicker bilayer film on the surface causing the sulphide film to be unstable, which is
also associated with the higher current in Figure 9-S. The thicker film formation
provides a better barrier to reduce the corrosion rate; however, it leads to a higher
acidic environment on the metal surface, which results in pitting propagation [6S,
lOS]. This is supported by the in-situ camera observation, which shows that the
205
solution turns milky in colour. An alternati ve postulation could be that at 200ppm it

generates a direct interaction with H 2S gas and Fe 2+ ion re sulting in the nullific ati on
of the corrosion inhibitor functi on to reduce the pitting propagation .
120 ..,
1-
100
:..-
....
~
SO (I S
;::::j
~
E
:i
..c
-
n 6 <-::....
,: "
-to ~
---
CL (I -I
C]) 0
0
~
20 .., 0
0.. 0- --'
0 (I
(I )0 100 1)0 2011
Inlubltol C\>llCc:lltl:ltWll (ppm )
~ A .YC: .-\.rtificial PIt - .-\Y C: Nahu al PIts -k- I.lUhal C~>ll~>;)wn rate:
Figure I 0-l7 : Corrosion rate and pit depth data on concentrati on profile for
Nonoxynol-6 phosphate inhi bitor on X65 carbon steel , 10% H 2S, 90 % e0 2 at 80 e 0
T his is supported by the FTIR resu lts, which show th at none of the inhibitor
elements were fo und on the fi lm area or pitting site. Figure 10-1 8 show s the
nonoxy nol-6 phosphate mec hanism on artificial pits based on the in -siru observati on
findings .
Artificial Pit
Material
.,/
... Inh ibitor
... Iron Carbide
Potentiostatic
•
Uncorroded Afte r 24 hou rs
(as pol ished)
Figure 10- 18: Nonoxynol-6 phosphate mec hani sm on X65 carbon steel , 10% H 2S.
90% CO 2 a t 80 0 e after 24 hours

206
It shows that at an effective concentration, nonoxynol-6 phosphate is attracted

2
to Fe + on or near the metal surface and on the film. Nonoxynol-6 phosphate will form
a monolayer, which governs the mechanism to reduce the general corrosion and
localised corrosion [65, 98]. It is very interesting to compare the nonoxynol-6
phosphate mechanism with the imidozoline mechanism in sweet environments.
Nonoxynol-6 phosphate belongs to the phosphate ester group of inhibitors; however,
both inhibitors show similar a mechanism in inhibiting general corrosion and
localised corrosion. This shows that both inhibitors could be classed as mixed
anodic/cathodic inhibitors due to their interaction with Fe 2+ and formation of an
inhibitor film at both the anodic and cathodic sites [196].
10.12 The effect of poly alkyl pyridines on artificial pit growth under
sweet conditions
Poly alkyl pyridine inhibitors belong to the imidazoline type inhibitor group
that was used in the sour condition. Figure 9-6 from the results chapter shows that the
inhibitor could greatly reduce the corrosion rate even at lower concentrations. This is
supported by Wang et aI., who shows that a 15ppm concentration of imidazoline type
inhibitor could reduce the risk of both a general and localised attack [139]. The
performance of the inhibitor to reduce the corrosion rate increases as the inhibitor
concentration increases, however, the pit depth analysis in Figure 9-15 shows that the
inhibitor promotes the pit propagation if the concentration is applied below the
minimum value required. A small difference between the average pit and maximum
pit depth for artificial pit and natural pit suggests that the inhibitor reaction was
similar across the surface. The inhibitor performed at optimum concentration at
200ppm to reduce the general corrosion rate and pitting attack, as shown in Figure 10-
19. However, at 25ppm, the inhibitor only provided protection for general corrosion
but not against pitting propagation. It is postulated that below the minimum
concentration required the inhibitor destructively adsorbed on colloidal iron sulphide,
which formed around the mouth of the pit [141]. This is supported by Marsh et aI.
who show that at 15ppm, the imidazoline group inhibitor only provides protection
against general corrosion but provides little protection against localised corrosion
[ 141]. Interestingly the FfIR analysis found the inhibitor element at the pit site area
for IOOppm and 200ppm, however, the inhibitor was absent for ~5ppm. This suggests
207
that above the mInImum concentration , the inhibitor actually adsorbed to th e pit
mouth area and onl y formed a protective inhibitor film at the pit si te. The FTIR re sults
show that none of the inhibitor elements we re fou nd on the film surface area away
from the pitting. The in- situ camera observation shows that the growth of iro n
sulphide film slows do wn for 100ppm and doe s not grow for 200ppm. Thi s sugge sts
that the inhibitor actually hinders the diffu sion control led growth of the iron sulphide
film on the surface and provides localised protection at the pit site [116] .
Figure 10-20 show s the poly alkyl pyridine mechani sm on ar1ificial pits based
on the finding s of the in-situ observation . It sho ws that at an effective concentration,
poly alkyl pyridine is attracted to Fe 2+ and low pH site s inside the artificial pits and
forms a film of inhibitor to provide protection to loca li sed corrosion and general
corrosion . It is very interesting to compare the po ly alkyl pyridine mec hani sm wi th
the phosphate ester mechani sm in sweet environments . Poly alkyl pyridine belongs to
the imidazoline group of inhibitors; however, both inhibitors show a simil ar
mechani sm. Both inhibitors inhibit the loc ali sed corrosion by blocking the anod ic
sites on the surface.
")
160 1 -
I-HI :....,
:...-.
12 0
0S @
::::
:::!
100 'tJ
I) 6 (":;
-B SO
:....,
,....
~ c::
'tJ 60 0 -I ~
Q 0
..... :....,
6: -10
:....,
") 0
0 - ,-
....)
20
I)
0
0 50 100 150 200
Inlubltcll COllcC'lltrZl twll (ppm )
~ .-\\'C' .-\ltlfiClal PIt -.- .-\\'C' Na tm,ll Pih - . - Imtral (\'l1\,':)l\.lllr ak
Figure 10- 19: Corrosion rate and pit depth data on conce ntrati on profile for pol y alkyl
pyridine inhibitors on X65 carbon steel , 10% H2S, 90% CO2 at 80

0
e
208
Artificial Pit
Material Inh ibitor
.... Iron Carbide
...
-
Potentiostatic
Uncorroded After 24 hours

(as polished)
Figure 10-20: Poly alkyl pyridine mec hani sm on X65 carbon steel, 10% H 2S, 900/c
CO 2 at 80°C after 24 hours
209
Chapter 11 Conclusion and future work
11.1 Conclusion
An extensive study on inhibition of pitting corrosion of carbon steel X65 in

sweet and sour conditions was carried out using the electrochemical technique and
post-test surface analysis techniques. The mechanisms related to the pitting behaviour
and inhibitor under sweet and sour conditions were identified and analysed. The
interaction between the corrosion film and inhibitor play an important role in reducing
and stopping pitting corrosion if the effective concentration of the inhibitor is applied
to the system. These important findings are summarised in the following sections.
11.1.1 In-situ visualisation rig and sour rig design and setup
• An in-situ visualisation technique was developed to monitor the film growth

and pitting process on X65 carbon steel surface under sweet and sour
conditions.
• It was possible to observe the film growth and early stages of natural pit
growth using an in-situ visualisation technique under sweet conditions. By
using this technique it was also possible to observe the interaction between the
corrosion inhibitor and corrosion product on the surface and at the pit site area
to understand the inhibitor mechanism. However, it was not possible to
monitor pitting propagation using this technique due to the extreme
experimental condition and the nature of carbon steel pitting covering the pits
with corrosion deposit.
• It was possible to observe the early stage of film growth usmg an in-situ
visualisation technique under sour conditions. It was also possible to observe
the interaction between the corrosion inhibitor and corrosion product on the
surface and at the pit site area using this technique to understand the inhibitor
mechanism. However, it was not possible to monitor pitting growth using this
technique due the nature of the iron sulphide film covering the pits.
210
• A sour corrosion rig was developed and was able to perform sour corrosion
experiments successfully and safely. The rig was equipped with an in-situ
visualization technique with an option to perform normal sour experiments.
This rig was also able to perform two experiments at a time and was equipped
with all the necessary safety equipment.
• In-situ visualisation experiments and normal sour experiments were

successfully performed using the sour corrosion rig to study localised
corrosion behaviour for X65 carbon steel.
• The artificial pit technique developed in this study was able to propagate under
sweet and sour conditions to a desired pit depth using the potentiostatic
method. This technique was also able to simulate the natural pitting
propagation under sweet and sour conditions with accelerated time duration.
11.1.2 Characterisation of the surface film formed from sweet and

sour corrosion.
• Surface analyses of early sweet and sour corrOSIOn products were studied
using SEM, FIB/SEM, AFM, EDX and XPS, SEM and FIB/SEM.
• The morphology of sweet films were studied from 0.5 to 72 hours and it was
observed that the corrosion film is denser and more compact on the external
part of the film and some porous structures at the bottom of the film.
• FIB-SEM observed that at 0.5 hours the cross-section shows a good bonding
between the film to the metal surface, which is denser and more compact at
the film interface and some porous structures at the base of the film adjacent to
the substrate.
• AFM analysis observed that the film morphology starts to become rough after
I hour due to the iron carbonate film build up filling the gap that is left from
the anodic process. SEM analysis also observed that the morphology of the
211
sweet film is denser and more compact on the external part of the film and
some porous structures at the bottom of the film.
• XPS analysis observed that the iron carbonate component is present and grows
at the external part of the sweet film followed by iron carbide growth under it
to make the film semi protective.
• Under sour conditions, iron sulphide is the predominant product for the 90°C
specimens and provides better protection compared to the 15°C specimens.
The studies also show that both iron carbonate and iron carbide are present in
the sour specimens.
• SEM analysis for the sour specimens observed that the films are composed of
two different layers. The base layer deposit grows across the material interface
uniformly and the second layer grows in scattered domains on the base layer.
11.1.3 Investigation of pitting corrosion in sweet and sour conditions.
• Under sweet conditions, the pitting process was studied at various times from
6 to 150 hours. Pits are able to initiate and propagate to around 66.31lm to
73.4ll m depth after 150 hours. The pits under the studied test conditions did
not show a consistent pit depth increase over time until 70 hours of immersing
time. However, tests at 96, 120 and 150 hours show a linear increase of pitting
depth over time.
• Under sour conditions, the pit depth recorded for the first 4 hours was around
8.9Il m . The pit propagates to around 31.4llm depth after 96 hours exposure
time.
• Pitting in sweet and sour will start propagating once the film formation
reaches a steady state condition.
212
• Both phosphate ester and irnidazoline inhibitors showed excellent performance

to stop pit propagation in sweet conditions if the effective concentration is
applied.
• Under the effective concentration of phosphate ester, there was no significant

different effect in terms of reducing the corrosion rate due to the iron
carbonate film that formed across the surface before the inhibitor was added.
• The effective concentration of irnidazoline showed good performance In
reducing the general corrosion rate.
11.1.4 Evaluation of inhibitor performance using artificial pit

technique under sweet conditions.
• The potentiostatic approach for artificial pits was studied under the sweet
conditions. It was found that it allows the artificial pit to propagate to around
48.9f.lm to 53.1f.lm after 24 hours.
• Both phosphate ester and imidazoline inhibitors showed excellent performance

to stop pit propagation if the effective concentration was applied.
• In-situ cameras were able to observe the formation of a black deposit on the
surface due to the underdose reaction of phosphate ester with the corrosion
product covering the artificial pits, which resulted in a favourable condition
for pits to grow. However if the effective concentration of phosphate ester
inhibitor is applied, it shows that the inhibitors stop the formation of the black
deposit.
• FfIR analysis is able to identify iron carbonate film on the blank specimens
and detect the presence of the inhibitor on the surface after the inhibitor test.
FfIR analysis reveals that phosphate ester inhibitors inhibit pits by adsorbing
the inhibitor at the pit site but are absent in the surrounding film. lmidazoline
213
inhibitor inhibits the pits by absorbing at the pit site and in the surrounding
film.
11.1.5 Evaluation of inhibitor performance using artificial pit

technique under sour conditions
• The potentiostatic approach for artificial pits was studied under sour
conditions. It allows the artificial pits to propagate to around 31.6/lm depth
after 24 hours.
• Both nonoxynol-6 phosphate and poly alkyl pyridine inhibitors showed

excellent performance to stop pit propagation if the effective concentration is
applied.
• Both nonoxynol-6 phosphate and poly alkyl pyridine inhibitors showed

excellent performance to reduce the corrosion rate.
• The in-situ camera observed that an iron sulphide film could cover most of the
surface in 60 minutes. However if the effective concentration of the inhibitor
is applied, it shows that the inhibitors actually delay and stop the formation of
the black film, which could be because of the iron sulphide.
• FfIR analysis is able to identify the iron sulphide film on the blank specimens
and detect the presence of the inhibitor on the surface after the inhibitor test.
The FfIR analysis reveals that the poly alkyl pyridine inhibitors inhibit pits by
absorbing the inhibitor at the pit site but are absent in the surrounding film.
Nonoxynol-6 phosphate inhibitor inhibits the pits by adsorbing at the pit site
and in the surrounding film.
2 14
11.3 Industrial relevance
• T he artificial pit technique developed in thi s stud y could be adapted to the

fie ld corrosion test coupon . This wi ll create a hot spot on the coupon. whi ch
could provide information about general corrosion and pitting corrosion.
• Figure 11-1 shows the inhibitor se lection recommendati on for pitting

corrosion inhibition fo r oil and gas X65 pipeline field application based on the
findings fro m this stud y.
Inhibitor
Before
treatment
.......
Imidazoline film
Iron Carbon ate
I ron Carbid e Imidazoline • Protect from
general corrosion
1-I, ..."
I.J.'j '" __ ••••••• , J.
• Preve nt pitting
growth
New X65 carbon steel pipeline under sweet conditions
Phospha te
ester film
Iron Carbonate J / .. . Phosphate ester • Stop pitting

propagation
Iron Carbi de ............ .
Low pH ........... . •
In service X65 carbon steel pipeline under sweet cond ition s
Nonoxynol-6
6 6
,," c'' '· ··O
..................... phosphate film
Iron Sul fide ............ Nonoxynol-6
phosphate • Protect from
general corrosion
• • Prevent pitting
growth
New X65 carbon steel pipeline under sour conditions
Iron Sulfide ................ 6 6 Poly alkyl • Stop pitti ng

Iron Carbi de ............. ~ pyridine propagation
LOWP H .................~
• • Prote ct from
general
corrosion
In service X65 carbon steel pipel ine under sou r cond itions
F igure 11-1 : Inhibitor selection reco mmendation for locali sed corrosion inhibition for
oil a nd gas X65 pipeline fie ld application

215
11.3 Recommendations for future research
• Further mechanistic studies for corrosion and pitting corrosion inhibitors in

sweet and sour conditions are able to identify the reacting species resulting
from the reaction on the surface, which may comprise both corrosion products
and corrosion inhibitors. A further mix of inhibitors needs to be done to
observe the effect on general corrosion and pitting corrosion to study the
mechanism of the action.
• The effect of pitting with the effective concentration of inhibitor is an

interesting area and a very important issue in field service. Further
investigation needs to be done relating to effective concentrations of inhibitor
to gain a better understanding of the mechanism of failure due to this problem.
• Further corrosion research on the sweet corrosion effect on sour corrosion in

X65 transmission pipeline applications is required since many sweet service
pipelines on file become sour service pipelines due to oil and gas reservoir
ageing. The characteristic of sour corrosion film needs comprehensive
investigation to identify the various types of iron sulphide to understand the
behaviour for those species towards the protectiveness of iron sulphide film
and localised corrosion.
• The need for further development in in-situ monitoring techniques is desirable

to investigate the film breakdown and pitting behaviour. In-situ cameras with
3D lens or 3D microscopes could identify the pit depth in-situ. The in-situ
monitoring can also be combined with the Localised Corrosion Technique
(LCM) developed by Baker Hughes to correlate the in-situ current peak with
the pitting activity observed by the in-situ camera with time.
• The artificial pit technique can be developed further to better understand the
pitting corrosion behaviour. The size of the artificial pit could be reduced to
2~m to allow for the growth in diameter. The artificial pit technique could also
be used in the study of stainless steel.

216
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Appendix
Appendix A: Operation and emergency procedure of sour rigs
1) Standard laboratory procedure should be observed whilst working III the

laboratory.
2) Prior to the start of any testing involving H 2S gas, a notice must be given to the
project supervisor, laboratory technician and one other member of the research
group, this is to ensure that an appropriate and immediate response be taken in
the case of a H 2S alarm.
3) Extreme care must be taken and a personal H 2S safety alarm must be carried and
switched on when entering the laboratory.
4) The alarm should be set to activate when the H 2S concentration inside the fume
cupboard is more then lOppm or if the H 2S concentration is more then 5ppm in
the laboratory area.
5) A sign "H2S Test in Progress" must be displayed on the Laboratory entrance
doors throughout the duration of the test.
6) When the H 2S alarm is activated, the laboratory should be evacuated
immediately. The cause of the alarm should be determined by checking the
information displayed on the control box mounted outside the laboratory.
7) A shut down valve should be automatically activated to cut off the H2S supply
when the limit set for the alarm is reached.
8) It is considered safe to re-enter the laboratory when the control box outside the
laboratory registers the H 2S level as being less than 1ppm.
9) The "Reset" on the control box is pressed once to deactivate the alarm
10) Pressing the "Reset" a second time re-energises the automatic shut down valve
to allow gas to pass through.
11) The H 2S gas supply is turned off using the valve on top of the cylinder.
12) All leaks should be made good if it is safe to do so.

233
Appendix B: Helium pressure test procedure for sour rig
1) Check that all parts of the equipment are safe and ready to use.
2) Test the pipeline (not experiment vessel) at 0.8 bar with helium and hold the
pressure for 10 minutes to check the connection.
3) Increase the test pressure to 1 bar to check the blow off valve is operating.
4) Finish the 1 bar helium pressure test and release the pressure
5) Fill the vessel with test solution.
6) Mount the specimen on the specimen holder
7) Insert test electrodes and test the electrode assembly in the vessel.
8) Check the O-ring position
9) Seal the test vessel.
10) Start the helium pressure test at 0.08 bar. Test the system with helium for 15
minutes. (Both inlet and outlet valves must be open to allow gas to flow through
the vessel and scrubber units but close the final exit valve to trap the pressure at
0.08 bar).
11) Observe any gas and solution leaking.
12) Observe the pressure gauge to make sure that the gauge remains constant and
that there is no leaking ..
13) Increase the test pressure to 0.1 bar to check the blow off valve is operating.
14) Finish the 0.1 bar helium pressure test.
15) Start the helium flow test. Test the system with helium for 15 minutes. (Both
inlet and outlet valves must be open to allow gas to flow through the vessel and
scrubber.
16) Observe any gas and solution leaking
17) Observe the pressure gauge to make sure there is no trapped pressure.
18) Finish the helium flow test.
234
Appendix C: Cleaning the scrubber procedure for sour rig
1) Switch on the heater and stirrer unit.

2) Allow the vessel to heat to 30°C.
3) Purge the vessel with N2 and the outlet gas should be routed to the scrubber unit
for at least 60 minutes.
4) Stop the N2 purging and slightly open the vent valve on top of the vessel lid and
inject the H 2 S scavenger and close back the valve.
5) Purge the vessel with N2, again for at least 15 minutes.
6) Stop purging and carefully check the presence of any residual H 2S in the vessel
using the alarm. If any appreciative amount of H 2 S, more then 5ppm, is present
close the valve and return to step 4.
7) Loosen the lid clip.
8) Lift the lid carefully from the vessel.
9) Empty the vessel. Dispose of the solution into a designated container. (The
solution in the container should be treated by additional H 2 S scavenger and
mixed with water to remove any H 2S in the solution prior to final disposal).

Inhibition of Pitting On Carbon Steel

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Inhibition of Pitting On Carbon Steel

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INHIBITION OF PITTING ON CARBON STEEL

Ismarullizam Mohd Ismail

Submitted in accordance with the requirements for the degree of

The University of Leeds

I am extremely grateful to my supervIsor, Professor Anne Neville for her

I would like to express my gratitude to University of Leeds, England and

I am grateful to the present and past members of iETSI Research Group

I would like to express my appreciation and dedicate this work to my beloved

In order to develop supenor localised corrosIOn inhibitors, a better

Acknowledgements ...................................................................................................... .ii

2.0 Fundamental theory ........................................................................................9

2.4 Free energy............................................................................................. 10

2.10.1 Mechanisms of pitting corrosion ............................................ .17

3.0 Literature review..................................................................................................20

3.6.2 Pyrite ..........................................................................................-1-2

5.0 Experimental section........................................................................................67

and sour conditions ...............................................................................68

6.0 Results - Characterisation of the surface film formed from sweet

6.6.2 Evolution of Fe 2p3/2 peaks .................................................... ) 03

7.0 Results - Investigation of pitting corrosion in sweet and sour

8.0 Results - Evaluation of inhibitor performance using artificial pit

9.0 Results - Evaluation of inhibitor performance using artificial pit

condition ................................................................................................. 198

sweet conditions ......................................................................................206

11.0 Conclusion and future work ...........................................................................209

and sour corrosion..................................................................... 210

conditions .................................................................................. 211

509c CO 2 • 60°C, pH 5 ............................................................................39

Figure 3-22: Schematic of two-compartment cell for pencil artificial pit

Figure 5-4: Nominal structure of phosphate ester inhibitor...................................}9

various temperatures ..............................................................................84

after 0.5 hours.........................................................................................86

after 70 hours.......................................................................................... 107

from 5 hours to 8 hours ......................................................................... .11 1

from 10 hours to 150 hours .................................................................. ) 12

of pits surface after 4 hours, b) Cross-section from 2D view pits after

ester ........................................................................................................ 121

Figure 8-2: Potentiostatic polarisation curve at .f hours to 24 hours on X65

of phosphate ester .................................................................................. 132

of phosphate este~ ................................................................................. 13 2

e) 50ppm, f) 25ppm, ............................................................................... 136

e) 50ppm, f) 25ppm, ............................................................................... 13 7

phosphate ester....................................................................................... 140

pressure with imidazoline...................................................................... 1.+2

CO 2 saturated 10% NaCI brine at 80°C, pH 5.65, 1000ppm Fe 2+

steel in 109c NaCI brine at 80°C and 109c H,S c

Figure 9-14: 3D image of profi1ometer analysis of artificial pit on X65 carbon

nonoxynol-6 phosphate; a) 2D view of pits surface at 100ppm,

alkyl pyridines........................................................................................ 163

of poly alkyl pyridines ............................................................................ 172

Figure 10-7: Schematic representation of pitting growth mechanism over time

Figure 10-18: Nonoxynol-6 phosphate mechanism on X65 carbon steel,

Table 8-3: Summary FTIR results for imidazoline inhibitor in different

Table 9-1: FTIR spectra assignments for sour condition_______________________________________ 165

Table 10-1: EDX on the sour film at 90°C ______________________________________________________________ .180

XPS X-Ray Photoelectron Spectroscopy

1.1 Overview of oilfield corrosion as a global challenge

1.2 Carbon steel X65 pipeline operation in oilfield industry

Figure 1-2: Locali sed corrosion in pipeline [16]

Figure 1-3 : Leaking in subsea pipeline due to intemal corrosion [16]

Generally , pitting corrosion is difficult to quantify in the fie ld or the laboratory

1.3 Carbon steel pitting in sweet environments

1.4 Carbon steel pitting in sour environments

2 HCO~ + 2e- ~ H 2 + 2 CO~ 3-5